BRPI0621468A2 - coating compositions, articles, and methods for coating articles - Google Patents

Abstract

COATING COMPOSITIONS, ARTICLES, AND METHODS FOR COVERING ARTICLES. Coating compositions, articles and methods of coating articles are provided. Coating compositions and methods provide moldable coatings resistant to abrasion when cured on a substrate. The articles can be formed after applying the coating compositions to a substrate and cured. Coatings are also provided, which can be dyed, resistant to abrasion.

Description

COATING COMPOSITIONS, ARTICLES, AND METHODS FOR COATING ARTICLES

Cross Reference to Related Orders

This request is in connection with PCT application number PCT / US2 005/03 6458 filed October 12, 2005 claiming priority for and any other benefit from United States Provisional Order serial number 60 / 618,014 filed October 12 which are hereby incorporated by reference in their entirety. This request is related to the United States request entitled "Coating Compositions, Articles and Methods of Coating Articles" filed March 31, 2006.

FIELD OF INVENTION

The present invention relates to coating composition, articles and methods of coating articles. More particularly, the present invention relates to stable coating compositions which provide abrasion resistant formable coatings when cured on a substrate. Additionally, the present invention relates to stable coating compositions which provide dyed, environmentally resistant, abrasion resistant coatings when cured on a substrate.

BACKGROUND

Glass glazing can be replaced with transparent materials such as plastic that do not shatter or are more resistant to shattering than glass. For example, transparent materials made from synthetic organic polymers are used in public transport vehicles such as trains, buses, taxis and airplanes. Eyeglass lenses and other optical instruments, as well as window panes for large buildings, may also employ clear, shatter-resistant plastic. Additionally, the lighter weight of these plastics compared to glass can be an added advantage, especially in the transportation industry where vehicle weight is a major factor in its fuel economy.

While clear plastics provide the main advantage of being sharper resistant, lighter than glass, and with design flexibility, a serious disadvantage lies in the ease with which these plastics are marked and scratched due to daily contact with abrasives such as cleaning equipment or dust. Marking results in poor visibility and poor aesthetics, and often requires replacement of the pane or lens or the like.

To improve the abrasion resistance of plastic, marking resistant coatings have been developed. The main disadvantage of such abrasion resistant compositions is that they may not be formable after curing. Poor buildability means that bending or working a coated article will often lead to cracking or cracking of the coating. As a consequence, articles must be coated after formation, which can lead to delays in time and transportation of uncoated articles which may inadvertently over abrasion in transit.

Additionally, it is often desired to provide dyeable coatings that have abrasion resistance. In particular, such coatings may be useful for tinted window applications and for ophthalmic applications. Many known coating compositions do not readily allow a tint to be added to the coating composition after the coating composition is cured on the substrate. The ability to add a hue to such cured coating composition is highly desirable.

Thus, there remains a need in the art for coatings with good abrasion resistance and buildability. In addition, a need remains in the art for coatings that exhibit abrasion resistance and dyeing ability.

SUMMARY OF THE INVENTION

In accordance with embodiments of the present invention, compositions are provided which when applied to a substrate and cured, provide the abrasion-resistant formable coating on the substrate. The compositions may comprise an aqueous-organic solvent mixture having hydrolysis products and partial condensates of at least one epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride. wherein at least one of the epoxy functional silane and the diol functional organopolysiloxane are present in a multifunctional crosslinker molar ratio of from about 10: 1 to about 1:10, and an amount of water sufficient to hydrolyze the functional silane. epoxy, diol functional organopolysiloxane, and multifunctional crosslinker. In one example, at least one epoxy functional silane, and diol functional organopolysiloxane, is present in a multifunctional crosslinker molar ratio of from about 2: 1 to about 1: 2. In another example, the coating may be formed to a radius of approximately 2.54 cm less than approximately 25.4 cm on a polycarbonate substrate. In a further example, the coating may be formed to a radius of approximately 7.62 cm to approximately 12.7 cm on a polycarbonate substrate.

In another example, the casing has a Taber number of less than approximately 10 percent after 50 turns of a Taber wheel; or a Taber number less than approximately 2 percent after 50 turns of a Taber wheel. In another example, the casing has a Taber number less than approximately 45 percent after 200 turns of a Taber wheel; or a Taber number less than approximately 15 percent after 200 spins of a Taber wheel.

In a further example, at least one of epoxy functional silane and diol functional organopolysiloxane comprises approximately 5 to approximately 93% by weight of the composition solids, and the multifunctional crosslinker comprises approximately 7 to approximately 95% by weight of the composition solids. . In another example, at least one of epoxy functional silane and diol functional silane comprises approximately 30 to about 70% by weight of the composition solids, and the multifunctional crosslinker comprises approximately 30 to about 70% by weight of the solids. of composition. In a further example, the constituent solvent of the aqueous-organic solvent mixture comprises approximately 40 to approximately 89% by weight of the composition. In yet another example, the constituent solvent of the aqueous-organic solvent mixture comprises approximately 65 to approximately 95% by weight of the composition.

In one example, the constituent solvent of the aqueous-organic solvent mixture is selected from an ether, a glycol or a glycol ether, a ketone, an ester, a glycol ether acetate, and combinations thereof. In another example, the constituent solvent of the aqueous-organic solvent mixture is selected from alcohols having the formula ROH where R is an alkyl group containing 1 to about 10 carbon atoms. In another example, the constituent solvent of the aqueous-organic solvent mixture is selected from glycols, ethers, glycol ethers having the formula R1- (OR2) x-OR1 where χ is 0, 1, 2, 3 or 4, R1 is hydrogen or an alkyl group containing from 1 to about 10 carbon atoms and R 2 is an alkylene group containing from 1 to about 10 carbon atoms and combinations thereof.

In other examples, the epoxy functional silane is represented by the formula R3xSi (OR4) 4_x, where: χ is an integer of 1, 2 or 3; R 3 is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof containing 1 to about 10 carbon atoms and having at least 1 epoxy functional group; R4 is H, an alkyl group containing 1 to about 5 carbon atoms, an acetyl group, a group -Si (OR5) 3 -y R6y where y is an integer of 0, 1, 2 or 3, and combinations thereof; R5 is H, an alkyl group containing 1 to about 5 carbon atoms, an acetyl group, or other group -Si (OR5) 3 -y R6y and combinations thereof; and R 6 is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof containing 1 to about 10 carbon atoms.

In further examples, the aqueous-organic solvent mixture further comprises an effective amount of a leveling agent for spreading the aqueous-organic solvent mixture on the substrate and providing substantially uniform contact of the aqueous-organic solvent mixture with the substrate. In another example, the composition further comprises at least one catalyst, at least one ultraviolet stabilizer, or at least one surfactant, and combinations thereof.

In other embodiments of the present invention, compositions are provided which when applied to a substrate and cured provide an abrasion-resistant formable coating on the substrate. The compositions may comprise an aqueous-organic solvent mixture having hydrolysis and partial condensate products of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides. and wherein the diol functional organopolysiloxane is present at a molar ratio for the multifunctional crosslinker of from about 10: 1 to about 1:10, and an amount of water sufficient to hydrolyze the diol functional organopolysiloxane and the multifunctional crosslinker. In one example, the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker.

According to further embodiments of the present invention, compositions are provided which when applied to a substrate and cured, provide an abrasion-resistant formable coating on the substrate. The compositions may comprise an aqueous-organic solvent mixture having hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides and silylated multifunctional anhydrides, and wherein at least one epoxy functional silane is present at a molar ratio to the multifunctional crosslinker of from about 10: 1 to about 1: 10, and an amount of water sufficient to hydrolyze the epoxy functional silane and multifunction crosslinker, wherein The composition contains at least one amount of tetrafunctional silanes, disilanes, and alkyl silanes insufficient to make the coating rigid on the substrate. In one example, the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of a diol functional organopolysiloxane and the multifunctional crosslinker.

According to still further embodiments of the present invention, compositions are provided which when applied to a substrate and cured, provide an abrasion resistant formable coating on the substrate. The compositions may comprise an aqueous-organic solvent mixture having hydrolysis and partial condensate products of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides. and wherein the epoxy functional silane is present in a molar to multifunctional crosslinker ratio of from about 10: 1 to about 1:10; sufficient water to hydrolyze the epoxy functional silane and the multifunctional crosslinker; and at least one between tetrafunctional silane and a disilane, wherein the epoxy functional silane is present in a molar ratio to at least one between tetrafunctional silane and disilane of at least about 5.5: 1. In one example, the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of a diol functional organopolysiloxane and the multifunctional crosslinker.

In another example, the tetrafunctional silane has a formula of Si (OR9) 4, where R9 is H, an alkyl group containing from 1 to about 5 carbon atoms and ethers thereof, a carboxylate (OR9), a -Si group (OR10) 3 where R10 is H, an alkyl group containing 1 to about 5 carbon atoms and ethers thereof, a carboxylate (OR10), or other group -Si (OR10) 3 and combinations thereof. In a further example, the disilane has a formula of (R11 "0) xR12" 3-xSi-R13 "y-SiR14" 3-x (OR "15) x; where x is 0, 1, 2 or 3 and y is Wherein R 12 and R 14 comprise H, an alkyl group containing from about 1 to about 10 carbon atoms, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl polyether group, and combinations thereof; R 11 and R 15 comprise H, an alkyl group containing approximately 1 to about 10 carbon atoms, an acetyl group, and combinations thereof, where y is 1 then R 13 comprises an alkylene group containing from approximately 1 to approximately 12 carbon atoms, a polyether alkylene containing approximately 1 to about 12 carbon atoms, an aryl group, an alkylene substituted aryl group, an alkylene group which may contain one or more olefins, S, or O, where if x is 0 then R 12 and R14 comprise Cl or Br, and where if y is 0 then there is a bond the direct silicon silicon.

According to further embodiments of the present invention there are provided compositions which when applied to a substrate and cured, provide an abrasion resistant formable coating on the substrate. The compositions may comprise an aqueous-organic solvent mixture having hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides and multifunctional anhydrides. wherein the epoxy functional silane is present in a molar ratio to the multifunctional crosslinker of from about 10: 1 to about 1:10; sufficient water to hydrolyze the epoxy functional silane and the multifunctional crosslinker; and at least one alkyl silane, wherein the epoxy functional silane is present in a molar ratio to at least one alkyl silane of at least approximately 2.5: 1.

In one example, the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of a diol functional organopolysiloxane and the multifunctional crosslinker. In another example, alkyl silane has a formula of R16xSi (OR17) 4-X where χ is a number of 1, 2 or 3; R 16 is H, or an alkyl group containing 1 to about 10 carbon atoms, a functionalized alkyl group, an alkylene group, an aryl group, a polyether alkoxy group and combinations thereof; R17 is H, an alkyl group containing from 1 to about 10 carbon atoms, an acetyl group; and combinations thereof.

In accordance with other embodiments of the present invention, compositions are provided which when applied to a substrate and cured, provide a formable and abrasion resistant coating on the substrate. The compositions may comprise an aqueous-organic solvent mixture having hydrolysis products and partial condensates of at least one epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, wherein the multifunctional crosslinker. is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein at least one epoxy functional silane is present in a multifunctional crosslinker molar ratio of from about 10: 1 to about 1:10; and an amount of water sufficient to hydrolyze the epoxy functional silane and multifunctional crosslinker, wherein the composition does not contain tetrafunctional silanes, disilanes and alkyl silanes. In one example, the aqueous-organic solvent mixture further comprises hydrolysis products and partial condensates of a diol functional organopolysiloxane and the multifunctional crosslinker.

In accordance with embodiments of the present invention, articles are provided. The articles comprise a substrate and an abrasion-resistant formable coating present on at least one surface of the substrate by curing a coating composition, comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of at least one of silane. epoxy functional and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein at least one between epoxy functional silane and diol functional organopolysiloxane is present in a molar ratio for the multifunctional crosslinker from about 10: 1 to about 1:10; and an amount of water sufficient to hydrolyze the epoxy functional silane, the diol functional organopolysiloxane, and the multifunctional crosslinker. In one example, at least one primer is arranged at least on one substrate surface between the substrate and the coating.

In accordance with further embodiments of the present invention, articles are provided. The articles may comprise a substrate and an abrasion-resistant formable coating present on at least one surface of the substrate by curing a coating composition comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of a functional organopolysiloxane. diol and at least one multifunctional crosslinker, the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the diol functional organopolysiloxane is present at a molar to multifunctional crosslinker ratio of approximately 10: 1 to about 1:10, and sufficient water to hydrolyze the diol functional organopolysiloxane and the multifunctional crosslinker.

In accordance with other embodiments of the present invention, articles are provided. The articles may comprise a substrate and an abrasion resistant formable coating present on at least one surface of the substrate by curing a coating composition, comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of a functional silane. epoxy and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein at least one functional epoxy silane is present at a molar ratio to the multifunctional crosslinker. from about 10: 1 to about 1:10, and an amount of water sufficient to hydrolyze the epoxy functional silane and the multifunctional crosslinker, wherein the composition contains at least one of insufficient tetrafunctional silanes, disilanes, and alkyl silanes. to make the coating hard on the substrate.

In accordance with embodiments of the present invention, articles are provided. The articles may comprise a substrate and an abrasion-resistant formable coating present on at least one substrate surface by curing a coating composition, comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of an epoxy functional silane at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the functional epoxy silane is present in a multifunctional crosslinker molar ratio of approximately 10: 1 to approximately 1:10; sufficient water to hydrolyze the epoxy functional silane and the multifunctional crosslinker; and at least one between tetrafunctional silane and disilane, wherein the epoxy functional silane is present in a molar ratio of at least one between tetrafunctional silane and disilane of at least approximately 5.5: 1.

In accordance with further embodiments of the present invention, articles are provided. The articles may comprise a substrate and an abrasion resistant formable coating present on at least one surface of the substrate by curing a coating composition, comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of a functional silane. epoxy and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a multifunctional crosslinker molar ratio of approximately 10: 1 to about 1:10; sufficient water to hydrolyze the epoxy functional silane and the multifunctional crosslinker; and at least one alkyl silane, wherein the epoxy functional silane is present in a molar ratio of at least one alkyl silane of at least approximately 2.5: 1.

In accordance with embodiments of the present invention, articles are provided. The articles may comprise a substrate and an abrasion-resistant formable coating present on at least one surface of the substrate by curing a coating composition, comprising: a mixture of organic-aqueous solvent having hydrolysis products and partial condensates of at least one silane. epoxy functional compound and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein at least one epoxy functional silane is present at a molar ratio to the multifunctional crosslinker. from about 10: 1 to about 1:10; and an amount of water sufficient to hydrolyze the epoxy functional silane and multifunctional crosslinker, wherein the composition does not contain tetrafunctional silanes, disilanes and alkyl silanes.

In accordance with embodiments of the present invention, formed articles are provided. The articles may comprise a formed substrate and an abrasion-resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently forming the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis and partial condensate products of at least one between epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein at least one of epoxy functional silane and diol functional organopolysiloxane is present in a multifunction crosslinker molar ratio of from about 10: 1 to about 1:10; and an amount of water sufficient to hydrolyze the epoxy functional silane, the diol functional organopolysiloxane, and the multifunctional crosslinker. In one example, the article formed further comprises at least one primer disposed on at least one substrate surface between the substrate and the coating.

In accordance with further embodiments of the present invention, formed articles are provided. The articles formed may comprise a formed substrate and an abrasion resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently forming the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein diol functional organopolysiloxane is present in a molar ratio for the multifunctional crosslinker from approximately 10: 1 to approximately 1:10, and sufficient water to hydrolyze the diol functional organopolysiloxane and multifunctional crosslinker.

In accordance with other embodiments of the present invention, formed articles are provided. The articles formed may comprise a formed substrate and an abrasion resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently forming the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis and partial condensate products of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein epoxy functional silane is present in a molar to multifunctional crosslinker ratio of from about 10: 1 to about 1:10; and an amount of water sufficient to hydrolyze the epoxy functional silane and the multifunctional crosslinker, wherein the composition contains at least one of tetrafunctional silanes, disilanes, and alkyl silanes insufficient to make the coating rigid on the substrate.

In accordance with embodiments of the present invention, formed articles are provided. The articles may comprise a formed substrate and an abrasion-resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently forming the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis and partial condensate products of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein epoxy functional silane is present in a molar to multifunctional crosslinker ratio of from about 10: 1 to about 1:10; sufficient water to hydrolyze the epoxy functional silane and the multifunctional crosslinker; and at least one between tetrafunctional silane and disilane, wherein the epoxy functional silane is present in a molar ratio to at least one between tetrafunctional silane and disilane of at least approximately 5.5: 1.

In accordance with embodiments of the present invention, formed articles are provided. The articles may comprise a formed substrate and an abrasion-resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently forming the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis and partial condensate products of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein epoxy functional silane is present in a molar to multifunctional crosslinker ratio of from about 10: 1 to about 1:10; sufficient water to hydrolyze the epoxy functional silane and the multifunctional crosslinker; and at least one alkyl silane, wherein the epoxy functional silane is present in a molar ratio to at least one alkyl silane of at least approximately 2.5: 1.

In accordance with embodiments of the present invention, formed articles are provided. The articles may comprise a formed substrate and an abrasion-resistant formable coating present on at least one surface of the substrate by applying a coating composition, curing the coating composition, and subsequently forming the substrate, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis and partial condensate products of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein epoxy functional silane is present in a molar to multifunctional crosslinker ratio of from about 10: 1 to about 1:10; and an amount of water sufficient to hydrolyze the epoxy functional silane and the multifunctional crosslinker; wherein the composition does not contain tetrafunctional silanes, disilanes and alkyl silanes.

In accordance with embodiments of the present invention processes are provided for providing abrasion resistant formable coatings. The processes may comprise applying a coating composition to a substrate; and curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis and partial condensate products of at least one epoxy functional silane and one dio functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein at least one of epoxy functional silane and diol functional organopolysiloxane is present in a molar to multifunctional crosslinker ratio of from about 10: 1 to about 1:10; and sufficient water to hydrolyze epoxy functional silane, diol functional organopolysiloxane and multifunctional crosslinker. In one example, the process further comprises the step of forming the coated substrate. In another example, the process further comprises applying a primer to the substrate before applying the coating composition to the substrate in the primer.

In accordance with embodiments of the present invention processes are provided for providing abrasion resistant formable coatings. The processes may comprise applying a coating composition to a substrate; and curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis and partial condensate products of at least one diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is. selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the diol functional organopolysiloxane is present in a multifunction crosslinker molar ratio of from about 10: 1 to about 1:10; and an amount of water sufficient to hydrolyze the diol functional organopolysiloxane and the multifunctional crosslinker.

In accordance with embodiments of the present invention processes are provided for providing abrasion resistant formable coatings. The processes comprise applying a coating composition to a substrate; and curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from. multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides and wherein the epoxy functional silane is present in a multifunction crosslinker molar ratio of from about 10: 1 to about 1:10; and an amount of water sufficient to hydrolyze the epoxy functional silane and the multifunctional crosslinker, wherein the composition contains at least one of tetrafunctional silanes, disilanes, and alkyl silanes insufficient to render the coating rigid on the substrate.

In accordance with embodiments of the present invention, processes are provided for providing an abrasion resistant formable coating. The processes comprise applying a coating composition to a substrate; and curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from. multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a multifunction crosslinker molar ratio of from about 10: 1 to about 1:10; sufficient water to hydrolyze the epoxy functional silane and the multifunctional crosslinker; and at least one between tetrafunctional silane and disilane, wherein the epoxy functional silane is present in a molar ratio to at least one between tetrafunctional silane and disilane of at least approximately 5.5: 1.

In accordance with embodiments of the present invention, processes are provided for providing an abrasion resistant formable coating. The processes comprise applying a coating composition to a substrate; and curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected. between multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the epoxy functional silane is present in a multifunction crosslinker molar ratio of from about 10: 1 to about 1:10; sufficient water to hydrolyze the epoxy functional silane and the multifunctional crosslinker; and at least one alkyl silane, wherein the epoxy functional silane is present in a molar ratio to at least one alkyl silane of at least approximately 2.5: 1.

In accordance with embodiments of the present invention, processes are provided for providing an abrasion resistant formable coating. The processes comprise applying a coating composition to a substrate; and curing the coating composition, wherein the coating composition comprises: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from. multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein at least one epoxy functional silane is present in a multifunctional crosslinker molar ratio of from about 10: 1 to about 1:10; and an amount of water sufficient to hydrolyze the epoxy functional silane and the multifunctional crosslinker; wherein the composition does not contain tetrafunctional silanes, disilanes and alkyl silanes.

According to still further embodiments of the present invention there are provided compositions which when applied to a substrate and cured, provide dyeable, transparent coatings on the substrate. The compositions comprise an aqueous-organic solvent mixture having hydrolysis products and partial condensates of at least one of an epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride. and wherein at least one of epoxy functional silane and diol functional organopolysiloxane is present in a multifunctional crosslinker molar ratio of from about 10: 1 to about 1:10; an amount of water sufficient to hydrolyze at least one between the epoxy functional silane and diol functional organopolysiloxane and multifunctional crosslinker; and a blocked isocyanate. In some examples, at least one of epoxy functional silane and diol functional organopolysiloxane is present in a multifunctional crosslinker molar ratio of from about 6: 1 to about 1: 6. In other examples, at least one of epoxy functional silane and diol functional organopolysiloxane is present in a multifunctional crosslinker molar ratio of from about 3: 1 to about 1: 3. In additional embodiments, the blocked isocyanate comprises from about 1 wt% to about 30 wt% of the coating composition solids, or from about 2 wt% to about 15 wt% of the coating composition solids, or from about 3 wt.% To approximately 10 wt.% Of the solids of the coating composition.

In some examples, the blocked isocyanate is selected from at least one of Desmodur Bl 3175, Desmodur Bl 3272, Desmodur Bl 3370, Desmodur Bl 3475, Desmodur Bl 4265, Trixene Bl 7982, Trixene Bl 7983, Trixene Bl 7984, Trixene Bl 7980, Trixene Bl 7960, and Trixene Bl 7950. In other examples, the blocked isocyanate comprises Desmodur Bl 3175. In additional examples, the coating has a Bayer number greater than approximately 1.5 or greater than approximately 2. Still in additional examples, The coating has no adhesion or crack failure according to the QUV A and QUV B method test conditions for at least 72 hours or at least 120 hours. In some cases, the constituent solvent of the aqueous-organic solvent mixture comprises approximately 40 to approximately 98% by weight of the composition. In some cases, the constituent solvent of the aqueous-organic solvent mixture is selected from an ether, a glycol or a glycol ether, a ketone, an ester, a glycol ether acetate, alcohols having the formula ROH where R is a group. of alkyl containing 1 to about 10 carbon atoms, and mixtures thereof. In other examples, the constituent solvent of the aqueous-organic solvent mixture is selected from glycols, ethers, glycol ethers having the formula R1- (OR2) x -OR1 where χ is 0, 1, 2, 3 or 4, R1 is hydrogen or an alkyl group containing from 1 to about 10 carbon atoms and R2 is an alkylene group containing from 1 to about 10 carbon atoms and combinations thereof.

In still further examples, the composition further comprises at least one of tetrafunctional silanes, disilanes and alkyl silanes. In other examples, the composition further comprises colloidal silica. In some cases, epoxy functional silane is represented by the formula R3xSi (OR4) 4_x, where: χ is an integer of 1, 2 or 3; R3 is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms and having at least 1 functional group epoxy; R4 is H, an alkyl group containing 1 approximately 5 carbon atoms, an acetyl group, a group -Si (OR5) 3-yR6y where y is an integer of 0, 1, 2 or 3, and combinations thereof ; R5 is H, an alkyl group containing from 1 to about 5 carbon atoms, an acetyl group, or other group -Si (OR5) 3yR6y and combinations thereof; and R 6 is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms.

According to still further embodiments, compositions are provided which when applied to a substrate and cured provide coatings which may be dyed transparent on the substrate. The compositions comprise an aqueous-organic solvent mixture having hydrolysis products and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides. and where the diol functional organopolysiloxane is present at a molar to multifunctional crosslinker ratio of from about 10: 1 to 1:10; sufficient water to hydrolyze the diol functional organopolysiloxane and the multifunctional crosslinker; and a blocked isocyanate. In some examples, the organic aqueous solvent mixture further comprises hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker.

In accordance with additional embodiments, articles are provided. The articles comprise a substrate and a dyeable coating formed on at least one surface of the substrate by curing a coating composition, comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of at least one of functional silane epoxy and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein at least one of epoxy functional silane and diol functional organopolysiloxane is present in a molar ratio to the multifunctional crosslinker from about 10: 1 to 1:10; an amount of water sufficient to hydrolyze at least one between epoxy functional silane and diol functional organopolysiloxane and the multifunctional crosslinker; and a blocked isocyanate. In some examples, the articles further comprise at least one primer disposed on at least one substrate surface between the substrate and the coating. In some cases, at least one primer comprises a polyurethane dispersion based primer or a polyurethane dispersion based primer having a crosslinking agent. In some examples, the crosslinking agent is selected from a blocked isocyanate, aziridine resin, epoxy resin, and melamine resin. In further examples, the polyurethane dispersion-based primer further comprises an ultraviolet light absorber. In some examples, the crosslinking agent comprises approximately 1% to approximately 30% by weight of the polyurethane dispersion based primer solids.

In additional examples, the dyeable coating has a thickness between about 0.2 μm and about 20 μm, or between approximately 1.5 μm and about 10 μm, or between approximately 2.5 μm and about 7 μm. In other examples, the substrate is selected from acrylic polymers, poly (ethylene terephthalate), polycarbonates, polyamides, polyimides, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride, butyrates, and poly (diethylene glycol-bis). - carbonate). In some cases, the substrate comprises a lens.

In accordance with additional embodiments, articles are provided. The articles comprise a substrate and a dyeable coating formed on at least one surface of the substrate by curing a coating composition, comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of a diol-functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the diol functional organopolysiloxane is present in a molar to multifunctional crosslinker ratio of approximately 10: 1 to 1:10; sufficient water to hydrolyze the diol functional organopolysiloxane and the multifunctional crosslinker; and a blocked isocyanate. In some cases, the coating composition includes at least one between tetrafunctional silane and disilane, and wherein the epoxy functional silane is present in a molar ratio to at least one of the tetrafunctional silane and disilane of at least approximately 5.5: 1. .

In still further embodiments, articles are provided. The articles comprise: a substrate, a primer arranged on at least one surface of the substrate, and a dyeable coating formed on at least a portion of the primer curing a coating composition, wherein: the coating composition comprises: a mixture an aqueous-organic solvent having hydrolysis and partial condensate products of at least one epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein at least one between epoxy functional silane and diol functional organopolysiloxane is present in a multifunctional crosslinker molar ratio of approximately 10: 1 to 1:10; and an amount of water sufficient to hydrolyze at least one between epoxy functional silane and diol functional organopolysiloxane and multifunctional crosslinker; The primer comprises a polyurethane dispersion based primer having a crosslinking agent. In some examples, the dyeable coating has no adhesion or cracking failure according to the QUV A method and the QUV B method test conditions for at least approximately 72 hours.

In accordance with further embodiments, articles are provided. The articles comprise a substrate, a primer arranged on at least one surface of the substrate, and a dyeable coating formed on at least a portion of the primer curing a coating composition, wherein: the coating composition comprises: a mixture of aqueous-organic solvent having hydrolysis and partial condensate products of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the diol functional organopolysiloxane is present at a molar to multifunctional crosslinker ratio of approximately 10: 1 to 1:10; an amount of water sufficient to hydrolyze the diol functional organopolysiloxane and multifunctional crosslinker; The primer comprises a polyurethane dispersion based primer having a crosslinking agent.

According to other embodiments, processes for dyeing are provided with an abrasion-resistant, dyeable transparent coating that is coated on at least one surface of a substrate. The processes comprise contacting at least one surface of a substrate with a coating composition which forms an abrasion resistant transparent coating, which may be dyed after cure, the coating composition comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of at least one between epoxy functional silane and diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a multifunctional anhydride, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and at least one between epoxy functional silane and diol functional organopolysiloxane is present in a multifunctional crosslinker molar ratio of from about 10: 1 to 1:10; and an amount of water sufficient to hydrolyze at least one of the epoxy functional silane and diol functional organopolysiloxane and multifunctional crosslinker; curing the coating composition on the substrate to form a dyed, abrasion resistant curable transparent coating; and dyeing the cured coating by dipping the coated surface of the substrate in a dye bath for a period of time sufficient for the cured coating to absorb or transmit to the substrate a desired amount of dye.

In some examples, the coating composition further comprises a blocked isocyanate. In other examples, the processes further comprise applying a primer to the substrate before applying the coating composition to the substrate in the primer. In still other cases, the primer comprises a polyurethane dispersion based primer or a polyurethane dispersion based primer having a crosslinking agent.

According to still further embodiments, processes are provided for dyeing an abrasion-resistant, dyeable transparent coating that is coated on at least one surface of a substrate. The processes comprise: contacting at least one surface of a substrate with a coating composition that forms an abrasion-resistant transparent coating, which may be dyed after curing, the coating composition comprising: an aqueous-organic solvent mixture having a coating product. hydrolysis and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silyl multifunctional anhydrides, and wherein the diol functional organopolysiloxane is present in a molar ratio for the multifunctional crosslinker from approximately 10: 1 to 1:10; and an amount of water sufficient to hydrolyze the diol functional organopolysiloxane and the multifunctional crosslinker; curing the coating composition on the substrate to form a dyed, abrasion resistant curable transparent coating; and dyeing the cured coating by dipping the coated surface of the substrate in a dye bath for a period of time sufficient for the cured coating to absorb or transmit to the substrate a desired amount of dye.

DETAILED DESCRIPTION OF MODES OF THE INVENTION

The present invention will now be described with occasional reference to specific embodiments of the invention. The present invention may, however, be incorporated in different forms and should not be construed as limited to the embodiments set forth herein. Instead, these modalities are provided so that this revelation is complete.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in describing the invention herein is to describe specific embodiments only and is not intended to limit the invention. As used in the description of the invention and the appended claims, the singular forms "one", "one", and "the, a" are also intended to include plural forms unless the context clearly indicates otherwise. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.

Unless otherwise expressly indicated, all numbers expressing ingredient amounts, properties such as molecular weight, reaction conditions, and so on as used in the description and claims are to be construed as being modified in all cases by the term " about". Therefore, unless otherwise indicated, the numerical properties set forth in the following description and claims are approximations which may vary depending upon the desired properties to be obtained in embodiments of the present invention. Although the numerical ranges and parameters exposing the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as accurately as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from errors found in their respective measurements.

The present invention relates to stable coating compositions which, when applied on a variety of substrates and cured, form abrasion resistant, formable coatings. For purposes of defining and describing the present invention, the term "stable" will be understood to refer to coating compositions that are usable for a period of time appropriate for a specific application. Furthermore, the present invention relates to coated articles, formed coated articles, and methods of forming coated articles. The coated articles may be formed in any appropriate manner. For example, the coated articles may be thermoformed. "Thermoforming" is a term well known in the plastics art describing the process of shaping thermoplastic sheets by heating them to softness, then forming the softened sheets into desired shapes using any suitable procedure such as molding, jigging or vacuum forming.

In other embodiments, the present invention relates to dyeable coating compositions which provide dyeing ability to substrates having substantially transparent coating compositions thereon, methods for dyeing such coated substrates as well as coating compositions which are capable of dyeing. be dyed, and articles coated with such a coating composition. More specifically, the present invention provides substantially transparent coating compositions having good abrasion resistance, good adhesion to substrates used in the ophthalmic industry and other dyeable substrate or coating industries, and dyeing / dyeing ability when applied to lenses and healed.

In accordance with embodiments of the present invention, a stable coating composition is provided which forms a formable, abrasion resistant coating. The coating composition is cured to form a transparent coating on a substrate. The coating composition comprises an aqueous-organic solvent mixture having hydrolysis and partial condensate products of at least one of at least one epoxy functional silane and at least one diol functional organopolysiloxane, or combinations thereof and at least one. multifunctional crosslinker to form an organopolysiloxane coating on a substrate. At least one of epoxy functional silane and diol functional organopolysiloxane is present in a molar ratio for the multifunctional crosslinker between approximately 10: 1 and approximately 1:10. In one example, at least one of epoxy functional silane and diol functional organopolysiloxane may be present in a multifunctional crosslinker molar ratio of from about 2: 1 to about 1: 2.

In one example, the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, silylated multifunctional carboxylic acids, and silylated multifunctional anhydrides, and combinations thereof. In another example, the multifunctional crosslinker is at least one silylated multifunctional anhydride or at least one silylated multifunctional carboxylic acid. The coating composition also contains sufficient water to hydrolyze at least one between epoxy functional silane and diol functional organopolysiloxane and multifunctional crosslinker.

The solvent component of the aqueous-organic solvent mixture may be present in any appropriate amount. For example, the solvent component of the aqueous-organic solvent mixture comprises about 40 to about 98% of the coating composition by weight. In another example, the solvent component of the aqueous-organic solvent mixture comprises approximately 65 to approximately 95% of the coating composition by weight. It will be understood by those skilled in the art that at least a part of the solvent component of the aqueous-organic solvent mixture may be formed as hydrolysis by-products of the reactions of the coating compositions. At least one of epoxy functional silane and diol functional organopolysiloxane may be present in any appropriate amount. For example, at least between epoxy functional silane and diol functional organopolysiloxane comprises approximately 5 to approximately 93% by weight of the total solids of the composition. In another example, at least one of epoxy functional silane and diol functional organopolysiloxane comprises approximately 30 to approximately 70% by weight of the total solids of the coating composition. The multifunctional crosslinker may be present in any appropriate amount. In one example, the multifunctional crosslinker comprises approximately 7 to approximately 95% by weight of the total solids of the composition. In another example, the multifunctional crosslinker comprises approximately 30 to approximately 70% by weight of the total solids of the coating composition.

In another embodiment of the present invention, the coating composition may include tetrafunctional silanes, disilanes, or other alkyl epoxy non-functional silanes. However, tetrafunctional silanes, disilanes, and other alkyl silanes are present in amounts insufficient to make the cured coating rigid. For purposes of defining and describing the present invention, the term "rigid" will be understood to refer to coatings that are not formable as defined herein. In one example, the coating composition has a molar ratio of at least one epoxy functional tetrafunctional silane of at least about 5.5: 1. In a further example, the coating composition has a molar ratio of at least one epoxy-disilane functional silane of at least about 5.5: 1. In another example, the coating composition has a molar ratio of at least one epoxy functional alkyl silane silane of at least about 2.5: 1. The amount of tetrafunctional silanes, disilanes, and other non-functional epoxy alkyl silanes that are incorporated into the coating compositions of the present invention may vary widely and will depend generally on the desired properties of the cured coating produced from the coating compositions, as well as desired stability of the coating compositions. Non-functional epoxy tetrafunctional silanes, disilanes, and alkyl silanes can improve the abrasion resistance, chemical resistance, and optical properties of cured coatings. In other embodiments of the present invention, the coating composition may include other additives such as anti-fog components, leveling agents, catalysts, etc., as will be further described herein.

To test abrasion resistance of coated substrates, any of a number of quantitative test methods may be employed, including the Taber Test (ASTM D-4060), Tumble Test, and Swing Sand Test (ASTM F735-81). ). In addition, there are several qualitative test methods that can be used to measure abrasion resistance, including the Steel Wool Test and the Eraser Test. In the Steel Wool Test and the Eraser Test, sample coated substrates are scratched under reproducible conditions (constant load, frequency, etc.). Scratched test samples are then compared and scored against standard samples. A semi-quantitative application of these test methods involves the use of an instrument, such as a spectrophotometer or a colorimeter, to measure scratches on the coated substrate as a dry mist gain.

The abrasion resistance measured from a cured coating on a substrate whether measured by the Taber Test, Steel Wool Test, Eraser Test, Tumble Test, Bayer Test, etc. It is a function in part of curing temperature, curing time, coating thickness, and substrate. In general, higher temperatures and longer cure times result in higher measured abrasion resistance. Normally, cure temperature and cure time are selected for substrate compatibility. However, sometimes curing temperatures and curing times below optimum are used due to process and / or equipment limitations. It will be appreciated by those skilled in the art that other variables, such as coating thickness and substrate nature, will also have an effect on the measured abrasion resistance. In general, for each substrate type and for each coating composition there will be an optimum coating thickness. Optimum cure temperature, cure time, coating thickness, and the like can be readily determined empirically by those skilled in the art. Taber Abrasion Testing is performed with a Taber Teledyne Model 5150 Abrasion Medium (Taber Industries, North Tonawanda, N.Y.) with an auxiliary load weight of 500 g and CS-IOF wheels (Taber Industries, North Tonawanda, N.Y.). Prior to measurement, the wheels are ground with ST-11 grinding stone (Taber Industries, North Tonawanda, N.Y.) Grinding is performed by 25 turns of the CS-IOF wheels on the grinding stone. The initial sample dry mist is recorded 4 times with a Haze-gard Plus (BYK-Gardner, Columbia, MD) equipped with a Taber Abrasion Holder (BYK-Gardner, Columbia, MD). After 50 cycles of the CS-10F wheels in the sample, dry mist is re-recorded 4 times with a Haze-gard Plus (BYK-Gardner, Columbia, MD) equipped with a Taber Abrasion Holder (BYK-Gardner, Columbia, MD). ). The average dry mist is then determined for the initial dry mist reading, the dry mist reading after 50 cycles, and after 200 cycles using the new CS-10F wheels available at least since July 2003. The difference between dry mist mediated readings at 50 and 200 cycles and the initial dry mist reading is then reported.

The Taber method is considered a semi-quantitative method for measuring abrasion resistance. The accuracy and precision of the method depends on several factors, including the condition of the CS-10F test wheels. Changes in the condition of the CS-10F test wheels can have a significant effect on the abrasion resistance test result. For example, a recent change by Taber Industries in the composition of the CS-10F wheels altered dry mist gain in standard samples of 1% dry mist and 5% dry mist in 100 and 500 cycles (reported as 1% / 5%) respectively to 7% and 25% respectively. Throughout the test conducted here, all samples were tested with the same set of new Taber CS-10F wheels. In accordance with embodiments of the present invention, coatings may have Taber numbers less than about 30%, less than approximately 10%, or less than approximately 5% for 50 cycles. According to other embodiments of the present invention, coatings may have Taber numbers less than approximately 2% for 50 cycles. In other examples, coatings may have Taber numbers less than about 45%, less than about 30%, or less than about 15% for 200 cycles.

The buildability of the coatings can be tested as follows. An oven with a glass plate is preheated to 165 ° C. "A 0.63cm (1/4 inch) coated, 5.08cm (2 inch) χ 17.80cm (7 inch) polycarbonate test sample (1/4 inch Lexan PC, Regai Plastics, Santa Fe Springs CA) is placed flat on the glass plate and heated at 165 ° C for 18 min The coating thickness can be approximately 1-20 microns or approximately 2-10 microns The sample is removed from the oven and immediately placed in a Cylindrical mandrel The forming capacity of the sample is classified by determining the minimum radius of the mandrel where no cracking, scaling or peeling of the coating is observed.For purposes of defining and describing the present invention, the terms "formable" and "forming capacity "will be understood to refer to cured coatings which may be curved within a radius of less than approximately 5.4 cm, in accordance with the above procedure. In one example, cured coatings may be curved within a radius of approximately 7, 62 cm and approximately 12.7 cm according to the above procedure without cracking or cracking of the coating.

The presence of water in an aqueous-organic solvent mixture is required to form hydrolysis products of the silane components of the mixture. The actual amount of water can vary greatly. Sufficient water is required to provide a suitably homogeneous coating mixture of hydrolysis products and partial condensates of the silane components of the coating composition with the other components added. It will be appreciated by those skilled in the art that this amount of water can be determined empirically.

The solvent constituent of the aqueous-organic solvent mixture of the coating compositions of the present invention may be any solvent or combination of solvents that are compatible with the components of the coating composition including, but not limited to, an epoxy functional silane, functional organopolysiloxane. diol, a non-functional epoxy silane, a tetrafunctional silane, a disilane, the solvent constituent of the aqueous-organic solvent mixture may be water, alcohol, ether, a glycol or glycol ether, a ketone, an ester , a glycol ether acetate, and combinations thereof. Suitable alcohols may be represented by the formula ROH where R is an alkyl group containing from 1 to about 10 carbon atoms. Some examples of alcohols useful in the application of the present invention are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, cyclohexanol, pentanol, octanol, decanol, and mixtures thereof.

Suitable glycols, ethers, glycol ethers may be represented by the formula R1- (OR2) x-OR1 where χ is 0, 1, 2, 3 or 4, R1 is hydrogen or an alkyl group containing from 1 to about 10 carbon atoms. carbon and R2 is an alkylene group containing from 1 to about 10 carbon atoms and combinations thereof.

Examples of glycols, ethers and glycol ethers having the formula defined above include, but are not limited to, di-n-butyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol methyl ether dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol and combinations thereof. In addition to the above, cyclic ethers such as tetrahydrofuran and dioxane are suitable ethers for the aqueous-organic solvent mixture. Examples of ketones suitable for the aqueous-organic solvent mixture include, but are not limited to: acetone, diacetone alcohol, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone and combinations thereof. Examples of suitable esters for the aqueous-organic solvent mixture include, but are not limited to, ethyl acetate, n-propyl acetate, n-butyl acetate and combinations thereof. Examples of suitable glycol ether acetates for the aqueous-organic solvent mixture include, but are not limited to, methyl propylene glycol ether acetate, dipropylene glycol methyl ether acetate, ethyl 3-ethoxy propionate, ether acetate of ethylene glycol and combinations thereof.

Any suitable epoxy functional silane, diol functional organopolysiloxane from a hydrolyzed epoxy functional silane, or a combination thereof may be used in the coating compositions of the present invention. For example, the diol functional epoxy functional silane or organopolysiloxane can be any diol functional epoxy functional silane or organopolysiloxane that is compatible with multifunctional carboxylic acid. For example, such epoxy functional silanes are represented by the formula R3xSi (OR4) 4-x where χ is an integer of 1, 2 or 3, R3 is H, an alkyl group, a functionalized alkyl group, a group of alkylene, an aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms and having at least 1 epoxy functional group, and R4 is H, an alkyl group containing from 1 to about 5 carbon atoms, an acetyl group, a group of -Si (OR5) 3 -yR6y where y is an integer of 0, 1, 2 or 3, and combinations thereof where R5 is H, an alkyl group containing of 1 to about 5 carbon atoms, an acetyl group, or other group of -Si (OR5) 3- yR6y and combinations thereof, and R6 is H, an alkyl group, a functionalized alkyl group, an alkylene group an aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms It may also contain an epoxy functional group.

In another example, diol functional organopolysiloxane is the product of an epoxy functional silane ring opening reaction with water. The ring opening reaction is accompanied by hydrolysis and condensation of the alkoxy groups. Such ring opening reaction is shown graphically as:

<formula> formula see original document page 45 </formula>

Where R is any appropriate group. In another example, a commercial source of a diol functional organopolysiloxane, HS2926, may be obtained from DEGUSSA Corp. (Piscataway, New Jersey). HS2926 may be used "as is" without further purification.

Diol functional organopolysiloxanes can be prepared by mixing an epoxy functional silane with an excess of water that is adjusted to a pH of three with acid and refluxed for several hours. The alcohol which forms during hydrolysis of the alkoxysilane groups may be distilled off.

Examples of suitable epoxy functional silanes include, but are not limited to, glycidoxy methyl trimethoxy silane, 3-glycidoxy propyl trihydroxy silane, 3-glycidoxy propyl dimethyl hydroxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl triethoxy silane, 3-glycidoxy propyl dimethoxy methyl silane, 3-glycidoxy propyl dimethyl methoxy silane, 3-glycidoxy propyl tributoxy silane, 1,3-bis (glycidoxy propyl) tetramethyl disiloxane, 1,3-bis (glycidoxy propyl) tetramethoxy disiloxane, 1,3 bis (glycidoxy propyl) -1,3-dimethyl-1,3-dimethoxy disiloxane, 2,3-epoxy propyl trimethoxy silane, 3,4-epoxy butyl trimethoxy silane, 6,7-heptyl epoxy trimethoxy silane, 9,10 -epoxy decyl trimethoxy silane, 1,3-bis (2,3-epoxy propyl) tetramethoxy disiloxane, 1,3-bis (6,7-epoxyheptyl) tetramethoxy disiloxane, 2- (3,4-epoxy cyclohexyl) ethyltrimethoxy silane, and the like.

Any suitable multifunctional crosslinker or combinations of multifunctional crosslinkers may be used in the present invention. The multifunctional crosslinker may be any multifunctional carboxylic acid, multifunctional anhydride, silylated multifunctional anhydride, silylated multifunctional carboxylic acid, and combinations thereof that are compatible with epoxy functional silanes, diol functional organopolysiloxanes, or other components of the coating compositions. Silylated multifunctional anhydrides and carboxylic acids have -Si (OR ') groups which are capable of interacting with hydrolysis products and partial condensates of epoxy functional silanes, diol functional organopolysiloxanes, tetrafunctional silanes, disilanes and alkyl silanes.

The multifunctional crosslinker may include, but is not limited to, multifunctional carboxylic acids as well as anhydrides that produce multifunctional carboxylic acids. The carboxylic acid functional compound can be represented by the formula R7 (COOR8) x, where χ is an integer of 1, 2, 3 or 4, and where R7 is selected from the group consisting of H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, a functionalized aryl group, an alkyl ether, and combinations thereof where each of the alkyl group, alkylene group, aryl group, functionalized alkyl group , and alkyl ether are further characterized as containing from 1 to about 10 carbon atoms, and where R 8 is selected from the group consisting of H, a formyl group, a carbonyl group, or an acyl group, where the group of acyl may be functionalized with an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, a functionalized aryl group, a functionalized alkyl group, an alkylene group, an aryl group, an of functionalized arila, an alkyl ether, and combinations thereof where each of the alkyl group, the functionalized alkyl group, the alkylene group, the aryl group, the functionalized aryl group, and the alkyl ether are further characterized as containing from 1 to about 10 carbon atoms. Examples of multifunctional carboxylic acids which may be employed in preparing the coating compositions of the present invention include, but are not limited to: malic acid, aconitic acid (eis, trans), itaconic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexyl succinic acid, 1,3,5 benzene tricarboxylic acid, 1,2,4,5 benzene tetracarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3 -cycloexanedicarboxylic acid, 1,1, -cyclohexanediacetic acid, 1,3-cyclohexanedicarboxylic acid, 1,1-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,3,5-cyclohexanedicarboxylic acid and unsaturated dibasic acids such as fumaric acid and maleic acid and combinations thereof.

Examples of multifunctional anhydrides which may be used in the coating compositions of the present invention include, but are not limited to, the aforementioned carboxylic acid anhydrides such as the above-mentioned dibasic acid cyclic anhydrides such as succinic anhydride, itaconic anhydride, glutaric anhydride, anhydride trimellitic, pyromellitic anhydride, phthalic anhydride, maleic anhydride, and combinations thereof.

The multifunctional crosslinker may also include, but is not limited to, a carboxylic acid or acid anhydride containing a -Si (OR ') group. An example of such material is 3-triethoxy silyl propyl succinic anhydride.

Optionally, in addition to the multifunctional crosslinker of the coating composition, a mineral acid such as hydrochloric acid or nitric acid may be used as a co-hydrolysis catalyst for the hydrolysis of the silane compounds described herein.

Any suitable tetrafunctional silane, or combination of tetrafunctional silanes, may be used in the present invention in amounts insufficient to render coatings rigid. For example, the tetrafunctional silane may have formulas of Si (OR9) 4, where R9 is H, an alkyl group containing from 1 to about 5 carbon atoms and ethers thereof, a -Si (OR10) 3 group where R10 is an H, an alkyl group containing from 1 to about 5 carbon atoms and ethers thereof, or another group -Si (OR10) 3 and combinations thereof. Examples of tetrafunctional silanes represented by the formula Si (OR9) 4 are tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetrabutyl orthosilicate, tetraisobutyl (tetraxy) methoxy (tetraxy) orthosilicate silane, tetrakis (ethoxy ethoxy) silane, tetrakis (methoxy ethoxy ethoxy) silane, trimethoxy ethoxy silane, dimethoxy diethoxy silane, triethoxy methoxy silane, poly (dimethoxy siloxane), poly (dimethoxy) diethoxy, tetrakis (trimethoxy siloxy) silane, tetrakis (triethoxy siloxy) silane, and the like. In addition to the substituents R 9 and R 10 described above for tetrafunctional silane, R 9 and R 10 taken with oxygen (0 R 9) and (OR 10) may be carboxylate groups. Examples of tetrafunctional carboxylate functional silanes are silicon tetracetate, silicon tetrapropionate and silicon tetrabutyrate.

The compositions may include any appropriate disilanes in amounts insufficient to render the coatings rigid. For example, disilanes may be represented by the formula (R10) xR12xSi-R13y-SiR143-x (OR15) x; where χ is 0, 1, 2 or 3 and y is 0 or 1; R 12 and R 14 are H, an alkyl group containing from about 1 to about 10 carbon atoms, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl polyether group, and combinations thereof; R 11 and R 15 are H, an alkyl group containing from about 1 to about 10 carbon atoms, an acetyl group, and combinations thereof. If y is 1 then R 13 may be an alkylene group containing from about 1 to about 12 carbon atoms, an alkylene polyether containing from about 1 to about 12 carbon atoms, an aryl group, an alkylene substituted aryl group, a alkylene group which may contain one or more olefins, S or O. If χ is O then R12 and R14 is Cl or Br. If y is 0 then there is a direct silicon-silicon bond. Examples of such disilanes include, but are not limited to, bis (triethoxy silyl) ethane, bis (triethoxy silyl) methane; bis (trichlorosyl) methane, bis (triethoxy silyl) ethylene, 1,3-bis (triethoxy silyl) ethane, hexaethoxy disiloxane and hexaethoxy disilane. The selection of the disilane as well as the amount of such disilane incorporated into the coating compositions will depend upon the specific properties to be improved or imparted to the coating composition or the cured coating composition.

The compositions may include any other appropriate alkyl silanes (i.e. trifunctional silanes, difunctional silanes, monofunctional silanes, and mixtures thereof, hereinafter referred to as silane additives) in amounts insufficient to render the coatings rigid. Alkyl silane additives which may be incorporated into the coating compositions of the present invention may have the formula R16xSi (OR17) 4.x where χ is a number of 1, 2 or 3; R 16 is H, or an alkyl group containing from 1 to about 10 carbon atoms, a functionalized alkyl group, an alkylene group, an aryl group, a polyether alkoxy group, and combinations thereof; R17 is H, an alkyl group containing from 1 to about 10 carbon atoms, an acetyl group, and combinations thereof.

Examples of silane additives represented by the formula defined above are methyl trimethoxy silane, ethyl trimethoxy silane, propyl trimethoxy silane, butyl trimethoxy silane, isobutyl trimethoxy silane, hexyl trimethoxy silane, octyl trimethoxy silane, decyl trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexane , 3-methacryloxy propyl trimethoxy silane, vinyl trimethoxy silane, allyl trimethoxy silane, dimethyl dimethoxy silane, 2- (3-cyclohexenyl) ethyl trimethoxy silane, 3-cyano propyl trimethoxy silane, 3-chloro propyl trimethoxy silane, 2-chloro ethyltrimethoxy silane, phenethyl trimethoxy silane, 3-mercapto propyl trimethoxy silane, 3-amino propyl trimethoxy silane, phenyl trimethoxy silane, 3-isocyanopropyl trimethoxy silane, N- (2-aminoethyl) -3-amino propyl trimethoxy silane, 4- (2 -aminoethyl amino methyl) phenethyl trimethoxy silane, chloromethyl triethoxy silane, 2-chloroethyl triethoxy silane, 3-chloro propyl triethoxy silane, phenyl triethoxy silane, ethyl triethoxy silane, propyl triethoxy silane, butyl triethoxy silane, isobutyl triethoxy silane, hexyl triethoxy silane, octyl triethoxy silane, decyl triethoxy silane, cyclohexyl triethoxy silane, cyclohexyl methyl triethoxy silane, 3-methacryloxy propyl triethoxy, allyl triethoxy silane, 2- (3-cyclohexenyl) ethyl triethoxy silane, 3-cyano propyl triethoxy silane, 3-methacrylamido propyl triethoxy silane, 3-methoxy propyl trimethoxy silane, 3-ethoxy propyl trimethoxy silane, 3-propoxy propyl trimethoxy silane 3-methoxy ethyl trimethoxy silane, 3-ethoxy ethyl trimethoxy silane, 3-propoxy ethyltrimethoxy silane. The selection of the silane additive as well as the amount of such silane additive incorporated into the coating compositions will depend upon the specific properties to be enhanced or imparted to the coating composition or cured coating composition.

In certain applications, it may be useful to add colloidal silica to the coating composition in insufficient amounts to make the cured coating rigid. Colloidal silica is commercially available under several different trade name names, including Nalco (Nalco Chemical Co., Naperville, IL); Nyacol (Nyacol Products, Inc., Ashland, MA); Snowtex (Nissan Chemical Industries LTD., Tokyo, Japan); Ludox (DuPont Company, Wilmington, Delaware); and Highlink OG (Clariant, Charlotte, NC). Colloidal silica is an aqueous or organic solvent dispersion of particulate silica and the various products differ mainly by particle size, silica concentration, pH, presence of stabilizing ions, solvent composition, and the like. It is understood by those skilled in the art that substantially different product properties can be obtained by selecting different colloidal silicas.

Colloidal silica, when added to a coating composition, is considered a reactive material. The silica surface is covered with silicon-bound hydroxyls, some of which are deprotonated, which may interact with materials in the coating composition. The extent of these interactions is determined by a variety of factors, including solvent system, pH, concentration, and ionic strength. The manufacturing process further affects these interactions. Those skilled in the art recognize that colloidal silica can be added to a coating formulation in different modes with different results. Colloidal silica may be added to the coating composition at any appropriate time.

The addition of colloidal silica to the coating compositions of the present invention may further increase the abrasion resistance of cured coating compositions and may further contribute to the overall stability of the coating compositions. Likewise, other metal oxides may be added to the coating compositions of the present invention. Such additions may be made in lieu of or in addition to any colloidal silica additions. Metal oxides may be added to inventive coatings to provide or enhance specific properties of the cured coating, such as abrasion resistance, refractive index, antistatic, anti-reflectance, weatherability, etc. Those skilled in the art recognize that the same types of reasons for including colloidal silica in the compositions of the present invention also apply more generally to the inclusion of metal oxides. Examples of metal oxides that may be used in the coating compositions of the present invention include silica, zirconia, titania, ceria, tin oxide and combinations thereof.

The amount of colloidal silica incorporated into the coating compositions of the present invention may vary widely and will depend generally on the desired properties of the cured coating produced from the coating compositions, as well as the desired stability of the coating compositions. Similarly, the amount of metal oxides incorporated into the coating compositions of the present invention may vary widely and will depend generally on the desired properties of the cured coating produced from the coating compositions, as well as the desired stability of the coating compositions. Colloidal silica and / or metal oxides will generally have a particle size in the range of 2 to 150 millimeters in diameter and more desirably, a particle size in the range of about 2 to 50 millimicons.

Although a catalyst is not an essential ingredient of the present invention, the addition of a catalyst may affect abrasion resistance and other coating properties including stability, porosity, cosmetics, caustic resistance, water resistance, etc. The amount of catalyst used may vary widely, but when present will generally be in an amount sufficient to provide from 0.1 to approximately 10% by weight based on the total solids of the coating composition.

Examples of catalysts that may be incorporated into the coating compositions of the present invention include, but are not limited to (i) metal acetyl acetonates, (ii) diamides, (iii) imidazoles, (iv) amines and ammonium salts, ( v) organic sulfonic acids and their amine salts, (vi) alkali metal salts of carboxylic acids, (vii) alkali metal hydroxides and (viii) fluoride salts. Thus examples of such catalysts include for group (i) such compounds as aluminum acetyl acetonates, zinc, iron and cobalt; for group (ii) dicyandiamide; for group (iii) such compounds as 2-methylimidazole, 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-propylimidazole; for group (iv) such compounds as benzyldimethyl amine, and 1,2-diaminocyclohexane; for group (v) such compounds as trifluoromethanesulfonic acid; for group (vi) such compounds as sodium acetate; for group (vii) such compounds as sodium hydroxide and potassium hydroxide; and for group (viii) such compounds as tetra n-butyl ammonium fluoride, and the like.

An effective amount of a flow control or leveling agent may be incorporated into the composition to more evenly spread or level the composition on the substrate surface and provide substantially uniform contact with the substrate. The amount of flow control or leveling agent may vary widely, but may be sufficient to provide the coating composition with about 10 to about 5,000 ppm flow control or leveling agent. Any conventional commercially available flow control or leveling agent that is compatible with the coating and substrate composition, which is capable of leveling the coating composition on a substrate, and which enhances wetting between the coating composition and the substrate may be employed. The use of flow and leveling control agents is well known in the art and has been described in the "Handbook of Coating Additives" (ed. Leonard J. Caibo, pub. Mareei Dekker), p. 119-145, the entirety of which is hereby expressly incorporated by reference in its entirety.

Examples of such flow control or leveling agents which may be incorporated into the coating compositions of the present invention include, but are not limited to, organic polyethers such as TRITON X-100, X-405, and Rohm and Haas N-57. , silicones as Ink Additive 3, Ink Additive 29, and Ink Additive 57 from Dow Corning, SILWET L-77 and SILWET L-7600 from Osi Specialties, and fluorotensives such as FLUORAD FC-4430 from 3M Corporation.

In addition, other additives may be added to the coating compositions of the present invention to enhance the usefulness of the coating compositions or the curing coatings of the coating compositions. For example, ultraviolet absorbers, antioxidants, and the like may be incorporated into the coating compositions of the present invention if desired.

In one embodiment, ultraviolet stabilizers may be added to the coating compositions.

Any suitable ultraviolet stabilizer and radical scavenger may be used in the present invention at any concentration effective to protect a substrate against light degrading effects. The use of these additives is described in the "Handbook of Coating Additives" (ed. Leonard J. Caibo, pub. Mareei Dekker), p. 225-269. In another embodiment, ultraviolet stabilizers may be added to the initiator compositions.

In another embodiment, a surfactant or surfactant mixture may be included in the coating compositions to provide the coated article with anti-fogging properties. The inclusion of surfactant results in a high wetting stress on the surface of the dry coating, and the high wetting tension prevents the formation of tiny droplets, i.e. fog, on the coating surface. The surfactant further increases the wetting of the water to maintain a clear, unblurry surface. An example of a suitable surfactant is Dioctyl sulfosuccinate, available as Aerosol OT 75 from Cytec Industries Inc, West Patterson, NJ. The surfactant component may be present in approximately 0.4 to 15% by weight of the coating composition. Higher levels may be used, however, they may result in increased dry mist, which may be undesirable for many applications. The anti-fogging effect of coatings can be measured by storing the surface cured article at 20 ° C, and then subjecting the coated article to saturated water vapor at 60 ° C. If the coated article becomes clear after 10 seconds and remains clear for at least 1 minute, the coating is anti-fog.

The coating compositions may be made in any appropriate manner. For example, at least one of epoxy functional silane and diol functional organopolysiloxane and multifunctional crosslinker may be added to a solvent and water and allowed to react at room temperature overnight. Additional additives such as leveling agent may then be added. The coating composition may be applied to a substrate and cured to form a coating.

According to embodiments of the present invention, an article may be provided. The article may comprise a substrate and a coating formed on at least one surface of the substrate by curing coating compositions of the present invention. Any suitable substrate may be coated with the coating compositions of the present invention. For example, plastic, wood, metal, printed surfaces, and leather materials may be coated. The compositions are especially useful as coatings for synthetic organic polymeric substrates in sheet or film form such as acrylic polymers, poly (ethylene terephthalate), polycarbonates, polyamides, polyimides, styrene-acrylonitrile-butadiene copolymers, chloride of polyvinyl, butyrates, and the like. Transparent polymeric materials coated with these compositions are useful as flat or curved enclosures such as windows, skylights and windshields, especially for transport equipment. Plastic lenses such as acrylic, poly (diethylene glycol allyl biscarbonate) (ADC) or polycarbonate lenses may also be coated with the compositions of the invention.

The coating compositions may be coated onto the substrates in any suitable manner. For example, the compositions of the invention may be applied to solid substrates by conventional methods, such as flow coating, spray coating, curtain coating, dipping coating, spin coating, roll coating, etc., to form a film. continuous surface.

By choosing the appropriate coating composition, application conditions and pretreatment (including the use of substrate primers), the coating compositions of the present invention may be adhered to substantially all solid surfaces. After applying the coating compositions of the present invention to solid substrates, the coatings may be heat cured at any appropriate temperature for any appropriate period of time. For example, coatings may be heat cured at temperatures in the range of 50 to 200 ° C or more for a period of seconds to 18 hours or more. It will be understood that the coatings may be cured in any other appropriate manner. For example, an ultraviolet activated photoinitiator capable of initiating cationic curing may be added such that the coating can be at least partially cured by ultraviolet light. It will be understood that coatings may subsequently be cured by another process such as a heat cure. Any suitable photoinitiator may be used. For example, aromatic onium salt or iron arene salt complexes available from Ciba Specialty Chemicals Corp., Terrytown, NY may be used.

The coating thickness may vary by the specific application technique, but coatings having a thickness of approximately 0.5 to 20 microns or approximately 1 to approximately 10 microns may be used. It will be understood that the coatings may be substantially transparent.

According to one embodiment of the present invention, the coating compositions may be applied to a substrate having a primer disposed thereon. Any appropriate primer may be used. For example, a polyurethane dispersion based primer may be used. Examples of such suitable primers are detailed in U.S. Patent No. 5,316,791, the entire contents of which are expressly incorporated herein by reference. An example of such an appropriate primer is PR1180 available from SDC Technologies, Inc., Anaheim, CA. In another example, the primer may be modified with ultraviolet light-absorbing substances and / or radical scavengers to increase the weatherability of the coated substrate. The primer may be applied to a substrate and thermally or air dried, for example air dried for less than approximately 2 hours, and the coating composition may subsequently be applied and cured, after which the coated substrate may be formed.

In accordance with further embodiments of the present invention, formed articles are provided. The articles formed comprise a substrate formed having a coating according to the present invention on at least one surface. The coating is applied to articles formed prior to article formation.

According to further embodiments of the present invention, dyed abrasion-resistant coating compositions, articles having dyed, abrasion-resistant cured coatings and processes for dyeing, dyed, transparent abrasion-resistant coatings which are coated by least on one surface of a substrate are provided. The coating compositions may be the coating compositions as described herein. The processes comprise contacting at least one surface of a substrate with a coating composition that forms an abrasion-resistant coating that can be dyed, transparent after curing, curing the coating composition on the substrate to form an abrasion-resistant coating that can be dyed. dyed, transparent, and dye the cured coating by dipping the coated surface of the substrate in a dye bath for a sufficient period of time for the cured coating to absorb or transmit to the substrate a desired amount of the dye.

The coating compositions may be the coating compositions described herein. In some examples, at least one of epoxy functional silane and diol functional organopolysiloxane is present in a multifunction crosslinker molar ratio of from about 10: 1 to about 1:10. In one example, at least one of epoxy functional silane and diol functional organopolysiloxane may be present in a multifunctional crosslinker molar ratio of from about 6: 1 to about 1: 6. In other examples, at least one of epoxy functional silane and diol functional organopolysiloxane may be present in a multifunctional crosslinker molar ratio of from about 3: 1 to about 1: 3.

In another example, at least one of epoxy functional silane and diol functional silane comprises approximately 11 to approximately 83% by weight of the composition solids, and the multifunctional crosslinker comprises approximately 17 to approximately 89% by weight of the composition solids. In another example, at least one of epoxy functional silane and diol functional silane comprises approximately 20 to about 70 wt% of the composition solids, and the multifunctional crosslinker comprises approximately 30 to about 80 wt% of the composition solids . In a further example, the solvent constituent of the aqueous-organic solvent mixture comprises from about 40 to about 98% by weight of the composition. In yet another example, the solvent constituent of the aqueous-organic solvent mixture comprises from about 50 to about 95% by weight of the composition.

In another embodiment of the present invention, the coating composition may include tetrafunctional silanes, disilanes or other alkyl silanes that are not epoxy functional in any appropriate amounts. It will be appreciated that for certain applications, tetrafunctional silanes, disilanes, or other alkyl silanes may be present in amounts that render the coating rigid or somewhat rigid. Suitable tetrafunctional silanes, disilanes or other alkyl silanes include those described herein. In additional embodiments, the compositions may include any other appropriate alkyl silanes (i.e. trifunctional silanes, difunctional silanes, monofunctional silanes, and mixtures thereof, hereinafter referred to as silane additives) in any appropriate amounts. Similarly, it is understood that for certain applications, tetrafunctional silanes, disilanes, or other alkyl silanes may be present in amounts that render the coating rigid or somewhat rigid. Suitable alkyl silanes include those described herein. In certain applications, it may be useful to add colloidal silica to the coating composition in appropriate amounts. It will be appreciated that for certain applications, colloidal silica may be present in amounts that render the coating rigid or somewhat rigid, and suitable colloidal silicas and uses include those described above.

It will be understood that the coating compositions may be applied in any appropriate manner. For example, the coating compositions may be applied to suitable substrates by conventional methods such as flow coating, spray coating, curtain coating, dipping coating, spin coating, roll coating, etc., to form a coating film. solid surface. The cured coating may be of any appropriate thickness. For example, the cured coating may have a thickness between approximately 0.2 μm to approximately 20 μm, approximately 1.5 μm to approximately 10 μm, or approximately 2.5 μm to approximately 7 μm. One skilled in the art would recognize that the thickness and / or solids content of the coating composition may be adjusted to provide a coating having an appropriate thickness and / or desired abrasion resistance.

Any suitable substrate may be coated with the coating compositions, and the coating compositions may be cured on a substrate to form an article having a cured coating, wherein the cured coating and / or the substrate may be dyed, and the coating may be dyed. Cured coating exhibits good abrasion resistance. For example, plastic, wood, metal, printed surfaces and leather materials may be coated. The compositions are especially useful as coatings for synthetic organic polymeric substrates in sheet or film form such as acrylic polymers, poly (ethylene terephthalate), polycarbonates, polyamides, polyimides, styrene-acrylonitrile-butadiene copolymers, chloride of polyvinyl, butyrates, and the like. Transparent polymeric materials coated with these compositions are useful as flat or curved enclosures such as windows, skylights and windshields, especially for transport equipment. Plastic lenses such as acrylic, poly (diethylene glycol allyl biscarbonate) (ADC), polycarbonate lenses, or polyamide, including nylon, may also be coated with the compositions of the invention. Useful polyamide for optical applications is available as a granulate from EMS-Chemie Inc. under the tradename Grilamid® or from Degussa Corp. under the tradename Trogamid®. For example, the coating compositions may be coated on ophthalmic lenses, such as prescription and non-prescription reading glasses, sunglasses and safety lenses. Ophthalmic lenses are made from a wide variety of raw materials, are generally distinguished by the refractive index and classified into low, medium and high index materials. An example for a low index material is CR 3 9®, the registered trade name by PPG Industries for ADC, a medium index material is also available from PPG Industries under the trade name Trivex®. High index raw materials are available from Mitsui Chemicals Inc. Japan in the trade name of its MR® series. These raw materials are cast by lens lens manufacturers and available under their specific trade names.

The dyeing step may be performed in any appropriate manner. For example, the surface of a cured coated substrate of the present invention may be immersed in a heated dye bath containing an appropriate colored dye, for example BPI Sun Gray or BPI Black, both are dyes sold by Brain Power Incorporated of Miami, Fia. The dye solution is prepared by diluting approximately one part BPI dye concentration to approximately ten parts water, and then heating the resulting solution to a temperature in the range of approximately 88 ° C to approximately 100 ° C while constantly stirring the solution. The coated surface of the substrate may be cleaned by cleaning with a compatible solvent prior to immersion in the dye bath for a period of time sufficient to absorb or impart the desired amount of dye, then washed with distilled water to remove excess dye and dried. . It will be appreciated by those skilled in the art that the intensity of the hue can be adjusted by varying the thickness of the coating or the time immersed in the dye bath. The degree of hue obtained can be determined using a colorimeter such as Gardner XL-835, which measures the percent light transmittance.

It is believed that a high amount of dye can be absorbed by the cured coating or transmitted to the substrate within a reasonable period of time. For example, in the ophthalmic industry, two levels of light transmittance ("LT") are generally used with regard to applying tint to eyeglass lenses. A 50% light transmittance means that the amount of dye absorbed or transmitted is sufficient to allow only 50% of the light to pass through the tinted lens. This is generally the light transmittance level applicable to "fashion" shades of glasses. A darker hue such as that used for sunglasses generally has approximately 20% light transmittance which means that the amount of dye absorbed or transmitted allows only 20% of light to pass through the lens. In some examples, ADC and Nylon coated lenses may be tinted at less than approximately 10% to approximately 20% light transmittance in approximately 15 to approximately 30 minutes.

In some instances, tinted lenses produced in accordance with such processes and / or utilizing such coating compositions exhibit environmental durability or improved weatherability. For example, tinted lenses may exhibit adhesion and crack resistance as tested by the Method A or Method B QUV accelerated wear test after approximately 72 or approximately 120 hours. The A QUV method test is performed according to the following procedure. For method A QUV, atmospheric accelerated wear testing, an AR Council procedure of UTP #: DUR-5.2.10, uniform testing procedure for environmental durability testing part A: QUV system, is followed . A QUV weather accelerated wear tester, available from Q panel corporation, 800 Canterbury Road, Cleveland, Ohio, is used. The QUV unit is set to repeat cycles of 4 hours of UV-A light exposure and 4 hours of condensation with a panel temperature of 55 ° C, QUV irradiance is set to 0.8 W / m2 / nm and calibrated. using a radiometer using the procedures outlined in the respective operating manuals. QUV test lenses are prepared according to the following procedures. Select an area on a lens with no coating defects. Using a cutting device, make six separate parallel cuts 1.5 mm ± 0.5 mm and approximately 15 to 20 mm long on the front (convex) surface of the lens to be exposed. Rotate the lens and make six parallel cuts 1.5 mm ± 0.5 mm 90 degrees from the first adjustment.

The test lenses are mounted on the lens holder with the test surfaces facing the UVA lamps. After 16 hours of exposure, the unit is stopped. Lenses are removed from the QUV, and examined on the exposed surface according to UTP #: APP-5.3.1 Standard Inspection Method to determine surface and material quality. The adhesion of the coatings is assessed by the trace test according to the following procedures. Apply a tape over the dashed pattern allowing one end of the tape to extend beyond the end of the lens by at least 4 inches. Rub back and forth several times on the tape surface over the dashed area to ensure good tape contact with the surface. Wait 90 seconds ± 30 seconds after applying the tape. While holding the lens tightly, grasp the extended end of the tape with your hand and quickly pull to the opposite side of the lens as close to 180 degrees as possible. Repeat the trace test twice more for a total of three ribbon pulls. Examine the dashed area according to UTP #: APP- 5.3.1 - Standard inspection method to determine surface and material quality. The test lenses are then returned to the QUV tester. The lens holder will be placed at different locations on the shelf compared to the starting position to account for tube to tube variability. The test steps are repeated daily for a total of 10 days. Coatings with good weatherability have no defects upon longer exposure to QUV.

The B QUV method test is performed according to the following procedure. For the B QUV method accelerated wear test, the ASTM G 53-88 procedure, standard practice for operating water and light (UV-fluorescent condensation type) exposure apparatus for exposure of non-metallic materials, is followed . A QUV accelerated wear tester, available from Q panei corporation, 800 Canterbury Road, Cleveland, Ohio, is used. The test procedure consists of 4 hours of exposure to UV-B light (at 48 ° C) followed by 4 hours of water vapor condensation (at 50 ° C). The cycle is continuously repeated for 120 hours. The QUV irradiance is adjusted to 0.8 W / m2 / nm and calibrated by a radiometer using the procedures outlined in the respective operating manuals.

QUV test lenses are prepared according to the following procedures. Clean the lens with alcohol using a soft Kleenex cloth. Dry it and observe its surfaces with the light projector to ensure that it no longer has any damage. Using a cutting device, make six separate parallel cuts 1.5 mm ± 0.5 mm and approximately 15 to 20 mm long on the front (convex) surface of the lens to be exposed. Rotate the lens and make six parallel cuts 1.5 mm ± 0.5 mm 90 degrees from the first adjustment. In the case of a standard lens (base curve ≤ 4,50), dashing is made between the two halves of the lens surface. In the case of a base curve ≥ 4.50 a third dash is required in the middle of the exposed surface. Load the lenses into the QUV lens holder in such a way that the dashed surface is turned into the QUV After 24 hours of exposure, the unit is stopped. The lenses are removed from the QUV, and examined on the exposed surface.

The adhesion of the coatings is assessed by the trace test according to the following procedures. Cut a strip of tape approximately 120-130 mm long and attach it securely to the lens surface covering the 2 dashed areas. Be sure to avoid any air bubbles between the lens surface and tape. Wait a minimum of 15-20 seconds and then pull out the tape to have a 90 ° angle between the tape and the lens surface. Repeat the trace test twice more for a total of three ribbon pulls. Examine the dashed area according to UTP #: APP-5.3.1- Standard inspection method to determine surface and material quality. The test lenses are then returned to the QUV tester. The lens holder will be placed at different locations on the shelf compared to the starting position to account for tube to tube variability. Coatings with good weatherability have no defects after longer exposure to QUV.

In some examples, dyed and / or undyed substrates produced in accordance with such processes exhibit good abrasion resistance. In some examples, the dyed or non-dyed substrates comprise lenses. For example, dyed or undyed substrates may have a Bayer number from greater than approximately 1.5 to greater than approximately 2 as tested according to the Bayer procedure. One of ordinary skill in the art would recognize that Bayer abrasion resistance depends on a number of factors including coating thickness, substrate material, and coating conditions. To test the abrasion resistance of Bayer coated substrates, a commercially available world (grain code 1524, file 12, ZF world) sold by Saint-Gobain Ceramic Materials of Canada, Inc., Niagara Falls, Ontario, is Used as abrasive material. In this test, 540 grams of alundo are loaded into a crib measuring 23.64cm (9 5/16 inches) by 17.14cm (6 3/4 inches), fitted with four lenses. Each set of four lenses, typically two poly (diethylene glycol-allyl biscarbonate) lenses, referred to herein as ADC lenses, and two coated lenses, are subjected to a 10.16 cm stroke (the direction of stroke coinciding with the cradle length (23.64cm (9 5/16 inches)) at an oscillation frequency of 300 strokes per minute for a total of 4 minutes. The lens cradle is repositioned by rotating 180 degrees after the initial 2 minute period of oscillation. Repositioning the cradle is used to reduce the impact of any inconsistencies in the swing mechanism. ADC reference lenses used are Silor 70mm Flat FSV lenses, purchased from Essilor of America, Inc. of St. Petersburg, Florida.

The procedure described above is slightly modified from that described by the AR Council of America by increasing the weight of the world to accommodate the increased surface area of the larger cradle. The cradle described above holds 4 lenses. The dry mist generated on the lens is then measured on a BYK Gardner HazeGard Plus dry mist meter. Dry mist gain for each lens was determined as the difference between the initial dry mist in the lens and the dry mist after testing. The ratio of dry mist gain in ADC reference lenses to dry mist gain over coated sample lenses was then reported as the abrasion resistance resulting from the coating material. A ratio greater than 1 indicates a coating that provides greater abrasion resistance than uncoated ADC reference lenses. The reason is commonly mentioned as the Bayer number. Higher abrasion resistance coatings have higher Bayer numbers than lower abrasion resistance coatings.

In other examples, dyed or undyed substrates may exhibit abrasion resistance rated as good, or better, as demonstrated by the steel wool test. The abrasion resistance of steel wool is evaluated according to the following procedure. The abrasion resistance of steel wool is assessed by YT-520, a commercially available instrument made by Yin Tsung Co. Ltd., Taiwan. The test is intended for the qualitative determination of scratch and abrasion resistance of uncoated and coated lens after rubbing with standard types of steel wool. The coated lens is cleaned with water or alcohol to remove surface contamination and dries completely. The lens is placed in the specimen holder and fixed by turning the screw to the left side. Type 0000 steel wool is selected and a small wad of steel wool, approximately 5.08 χ 5.08 cm, is prepared as the abrasive medium. Steel wool is loaded on the steel wool holder. 1000 grams of stainless steel weights are placed on the weight support. After 10 test cycles, the specimen lens is removed from the specimen holder, cleaned again using water or alcohol, and classified according to the following criteria: excellent - no visible scratch; good - slightly visible scratch; reasonable - moderate scratch; and bad - serious scratch.

In some examples, the processes may further include applying a primer to the substrate before contacting at least one substrate surface with the coating composition. In some examples, articles may comprise substrates having a primer disposed thereon and a cured coating disposed at least in a portion of the primer. The primer may be at least one of the polyurethane dispersion based primer as described herein. The primer may be applied to a substrate and thermally or air dried, for example air dried for a period of less than approximately 2 hours, and the coating composition may subsequently be applied and cured. In other examples, polyurethane dispersion based primers may further include a suitable crosslinking agent to promote adhesion of the coating to the substrate. For example, the crosslinking agent may comprise a blocked isocyanate and / or aziridine, epoxy and melamine resins. Aziridine, epoxy and melamine resins may react very slowly at room temperature with the polyurethane dispersion of the polyurethane dispersion-based primer. Resins may need to be used as a two-part system or must be used within a short time from manufacture. Examples of such resins include, but are not limited to: Neoresin CX100 aziridine resin, Cytec Cymel 303 and Cytec Cymel 385 melamine resins, and GE Silicones A-186 and CIBA Araldite ECN 1400 epoxy resins. In other examples the cross-linking agent may comprise blocked isocyanate Baxenden BI 7986; and such blocked isocyanate may be dispersed in water for use in the polyurethane dispersion of the polyurethane dispersion based primer.

The crosslinking agent may be provided in any appropriate amount. For example, the crosslinking agent may comprise approximately 1 to approximately 30 percent, approximately 1% to approximately 20 percent, or approximately 5% to approximately 15% of the primer composition by weight of the solids of the primer composition. The addition of the crosslinking agent to the primer is believed to improve the adhesion of the cured coating to the substrate and the environmental durability or wearability of the cured atmospheric coating. In further examples, the polyurethane dispersion-based primer may further include an ultraviolet light absorber (UVA) as described herein. The ultraviolet light absorber (UVA) can be supplied in any quantity. For example, UVA may comprise approximately 0.5% to approximately 40 percent, approximately 1% to approximately 20 percent, or approximately 5% to approximately 15% of the weight solids primer composition.

According to other embodiments of the present invention, compositions are provided which when applied to a substrate and cured provide a coating that can be dyed transparent to the substrate. Additionally, articles and processes involving the coatings are provided. The compositions are as described herein with the addition of at least one appropriate blocked isocyanate. In particular, the compositions are as described herein with reference to the dyeable coatings. Appropriate blocked isocyanates are believed to result in improved environmental durability or wearability by improved coating action. Examples of suitable blocked isocyanates include, but are not limited to, Desmodur Bl 3175, Desmodur Bl 3272, Desmodur Bl 3370, Desmodur Bl 3475 and Desmodur Bl 4265 available from Bayer and Trixene BI 7982, Trixene BI 7983, Trixene BI 7984 , Trixene BI 7980, Trixene BI 7960, Trixene BI 7950 available from Baxender LLC. Blocked isocyanates may be supplied in any appropriate amount. For example, blocked isocyanates may comprise approximately 1 wt% to approximately 30 wt% of the coating composition solids. In other examples, blocked isocyanates may comprise from about 2% to about 15% by weight of the coating composition solids or from about 2% to about 10% by weight of the coating composition solids.

The coating composition having blocked isocyanates may be applied to any suitable substrate to form a cured coating of any appropriate thickness in any appropriate manner. For example, plastic, wood, metal, printed surfaces and leather materials may be coated. The compositions are especially useful as coatings for synthetic organic polymeric substrates in sheet or film form, such as acrylic polymers, poly (ethylene terephthalate), polycarbonates, polyamides, polyimides, acrylonitrile styrene copolymers, styrene acrylonitrile butadiene copolymers, chloride of polyvinyl, butyrates, and the like. Transparent polymeric materials coated with these compositions are useful as flat or curved enclosures such as windows, skylights and windshields, especially for transport equipment. Plastic lenses such as acrylic, poly (diethylene glycol allyl biscarbonate) (ADC), polycarbonate lenses, or polyamide, including nylon, may also be coated with the compositions of the invention. Useful polyamide for optical applications is available as a granulate from EMS-Chemie Inc. under the tradename Grilamid® or from Degussa Corp. under the tradename Trogamid®. For example, the coating compositions may be coated on ophthalmic lenses, such as prescription and non-prescription reading glasses, sunglasses and safety lenses. Ophthalmic lenses are made from a wide variety of raw materials, are generally distinguished by the refractive index and classified into low, medium and high index materials. An example for a low index material is CR 3 9®, the registered trade name by PPG Industries for ADC, a medium index material is also available from PPG Industries under the trade name Trivex®. High index raw materials are available from Mitsui Chemicals Inc. Japan in the trade name of its MR® series. These raw materials are cast by lens lens manufacturers and available under their specific trade names. The coating may be applied by any appropriate methods as discussed herein.

In other examples, the coating composition having blocked isocyanates may be applied to a substrate such that the cured coating may have a thickness between approximately 0.2 μm and approximately 20 μm, approximately 1.5 μm to approximately 10 μm, or approximately 2.5 μm to approximately 7 μm. One skilled in the art would recognize that the solids content and / or coating thickness of the coating composition may be adjusted to provide a coating having an appropriate coating thickness and / or desired abrasion resistance. In some examples, the cured coating may have a Bayer number greater than approximately 1.5 or greater than approximately 2 as measured according to the Bayer test procedure discussed above. In other examples, the cured coating may have good abrasion resistance as determined by the steel wool test. In some examples, the cured coating formed from the coating composition having blocked isocyanates may exhibit adhesion and crack failure resistance as tested by method A or method B QUV after approximately 72 hours or after approximately 120 hours. Cured coatings and / or substrates having a cured coating formed from the coating compositions having blocked isocyanates may be applied and dyed according to the processes described herein. In some examples, a primer may be applied to a substrate prior to application of the coating composition having the isocyanate blocked, as discussed herein. The primer may be the primers discussed here.

EXAMPLE

The following examples are for illustration purposes only and are not intended to limit the scope of the claims that are appended hereto. All references cited herein are specifically incorporated by reference.

Example 1: Preparation of a diol functional organopolysiloxane

1000 g of 3-glycidoxy propyl trimethoxy silane epoxy functional silane (A-187, Witco Corporation, Greenwich, CT) was added to a 5 liter glass flask fitted with a distillation apparatus. A mixture of 40 g HCl (0.05 N) and 2960 g deionized water was then added to the 5 liter flask. The solution was then heated to reflux. After 3 hours of reflux, 743 g of solvent was distilled off. The product was used "as is" without further purification. Example 2: Coating and Primer Composition

7.5 grams of deionized water (DI) was added dropwise to a stirring solution of 15.0 grams of A-187, 19.3 grams of dihydro-3- (3- (triethoxy silyl) propyl multifunctional anhydride). ) - 2,5-furandione (GF20, Wacker chemical Corporation, Adrian, MI) and 140.0 grams of isopropanol solvent. The mixture was stirred at room temperature overnight. 0.18 grams of a PA-57 leveling agent solution (Downing Corporation, Midland, MI), 10 wt% propylene glycol monomethyl ether (PM ether, Ashland Chemical, Columbus, OH) was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating to a 1/4 inch thick polycarbonate plate initiated PR-1180 (SDC Technologies, Inc., Anaheim, CA). After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. The dry mist gain results from. A Taber test using CS-10F wheels according to the procedure outlined here were: 1.7% dry mist at 50 turns and 7.5% dry mist after 200 turns. Topcoat thickness was 3.5 microns. The buildability of the coating was assessed as described herein on a cylindrical mandrel and no cracks were observed within the 5 inch radius. Example 3: Coating composition and primer 8.0 grams DI water were added dropwise to a stirring solution of 17.7 grams A-187, 15.2 grams GF20, and 14 0.0 grams isopropanol. . The mixture was stirred at room temperature overnight. 0.18 grams of a 10% by weight solution of PA-57 in PM glycol ether was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 1/4 inch thick polycarbonate plate initiated by PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 2.3% dry mist at 50 turns and 11.4% dry mist after 200 turns. Topcoat thickness was 3.5 microns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracking was observed within 4 inches.

Example 4: Coating composition and primer 17.0 grams of DI water were added dropwise to a stirring solution of 4.5 grams of A-18 7, 2.9 grams of GF20, and 280.0 grams of isopropanol. The mixture was stirred at room temperature overnight. 0.37 grams of a 10% by weight solution of PA-57 in PM glycol ether was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 3.1% dry mist at 50 turns and 17.2% dry mist after 200 turns. Topcoat thickness was 3.2 microns. Coating ability was assessed on a cylindrical mandrel and no cracking was observed within 2 inches (5.08cm).

Example 5: Coating composition and primer 16.0 grams of DI water were added dropwise to a stirring solution of 47.0 grams of A-187, 2.0 grams of GF20, and 28.0.0 grams of isopropanol. The mixture was stirred at room temperature overnight. 0.36 grams of a 10% by weight solution of PA-57 in PM glycol ether was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 5.3% dry mist at 50 turns and 38.1% dry mist after 200 turns. Topcoat thickness was 3.1 microns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

Example 6: Coating composition and primer 15.0 grams of DI water were added dropwise to a stirring solution of 47.0 grams of A-187, 15.0 grams of GF20, and 260.0 grams of isopropanol. The mixture was stirred at room temperature overnight. 0.34 grams of a 10% by weight solution of PA-57 in PM glycol ether was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 6.0% dry mist at 50 turns and 59.1% dry mist after 200 turns. Topcoat thickness was 3.2 microns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

Example 7: Coating composition and primer 14.3 grams DI water were added dropwise to a stirring solution of 30.0 grams A-187, 38.6 grams GF20, and 300.0 grams ether solvent glycol PM (PMOH). The mixture was stirred at room temperature for three days. 0.38 grams of a 10 wt% solution of PA-57 in PMOH was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 3.0% dry mist at 50 turns and 14.0% dry mist after 200 turns. Topcoat thickness was 3.0 microns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

Example 8: Coating composition and primer 16.2 grams of DI water were added dropwise to a stirring solution of 4.5 grams of A-18 7, 29.0 grams of GF20, and 300.0 grams of solvent. of glycol ether PM (PMOH). The mixture was stirred at room temperature for three days. 0.39 grams of a 10 wt% solution of PA-57 in PMOH was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 4.7% dry mist at 50 turns and 26.7% dry mist after 200 turns. Topcoat thickness was 3.0 microns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

Example 9: Coating composition and primer 15.8 grams of DI water were added dropwise to a stirring solution of 47.2 grams of A-187, 2 0.3 grams of GF20, and 300.0 grams of solvent. PM glycol ether (PMOH). The mixture was stirred at room temperature for three days. 0.38 grams of a 10 wt% solution of PA-57 in PMOH was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 5.8% dry mist at 50 turns and 34.5% dry mist after 200 turns. Topcoat thickness was 3.0 microns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

Example 10: Coating composition and primer 15.0 grams DI water were added dropwise to a stirring solution of 47.2 grams A-187, 15.2 grams GF20, and 265.0 grams ether solvent glycol PM (PMOH). The mixture was stirred at room temperature for three days. 0.34 grams of a 10 wt% solution of PA-57 in PMOH was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 6.4% dry mist at 50 turns and 57.2% dry mist after 200 turns. Topcoat thickness was 3.0 microns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

Example 11: Coating composition and primer 2.7 grams DI water were added dropwise to a stirring solution of 3.8 grams A-187, 9.7 grams GF20, and 55 grams isopropanol / glycol ether PM (1: 1). The mixture was stirred at room temperature for three days. 0.08 grams of a 10 wt% solution of PA-57 in PM glycol ether was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 1.6% dry mist at 50 turns and 5.6% dry mist after 200 turns. Topcoat thickness was 3.2 microns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 6 inch radius.

Example 12: Coating composition and primer 4.0 grams of DI water was added dropwise to a stirring solution of 15.0 grams of A-187, 1.8 grams of itaconic acid crosslinker, and 75.0 grams of isopropanol. The mixture was stirred at room temperature overnight. 0.10 grams of a 10 wt% solution of PA-57 in PMOH was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 13.3% dry mist at 50 turns and 67.2% dry mist after 200 turns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

Example 13: Coating composition and primer 4.0 grams DI water were added dropwise to a stirring solution of 15.0 grams A-187, 1.4 grams succinic anhydride crosslinker, and 70.0 grams isopropanol. The mixture was stirred at room temperature overnight. 0.10 grams of a 10 wt% solution of PA-57 in PMOH was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 36.2% dry mist at 50 turns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius. Example 14: Coating composition and primer 4.0 grams DI water were added dropwise to a stirring solution of 15.0 grams A-187, 1.4 grams succinic anhydride, and 70.0 grams glycol ether PM (PMOH). The mixture was stirred at room temperature for three days. 0.10 grams of a 10 wt% solution of PA-57 in PMOH was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 42.0% dry mist at 50 turns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

Example 15: Coating Composition and Primer A mixture of 15.0 grams of trimethoxy (3-oxiranylmethoxy) propyl silane hydrolyzed aqueous solution available as HS2926 (SIVENTO INC., Piscataway, NJ), 9.66 grams of GF20, and 70 0.0 grams of isopropanol was stirred at room temperature overnight. 0.10 grams of a 10% by weight solution of PA-57 in PM glycol ether was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing. This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 1.0% dry mist at 50 turns and 3.0% dry mist after 200 turns. Topcoat thickness was 3.0 microns. Coating ability was assessed on a cylindrical mandrel and no cracks were observed within the radius of 17.80 cm (7 inches).

Example 16: Coating Composition and Primer A mixture of 15.0 grams of HS2926, 9.66 grams of GF20, and 70.0 grams of glycol PM ether was stirred at room temperature overnight. 0.10 grams of a 10% by weight solution of PA-57 in PM glycol ether was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing. This coating composition was cured at room temperature for 5 days prior to coating application. The coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 1.34% dry mist at 50 turns and 4.19% dry mist after 200 turns. Topcoat thickness was 3.0 microns. Coating ability was assessed on a cylindrical mandrel and no cracks were observed within the radius of 17.80 cm (7 inches).

Example 17: Coating Composition and Primer A mixture of 15.0 grams of HS2926, 0.7 grams of succinic anhydride, and 30.0 grams of isopropanol was stirred at room temperature overnight. 0.05 grams of a 10% by weight solution of PA-57 in PMOH was added. The composition was allowed to stir for an additional 20 minutes after the addition of PA-57 to ensure mixing. This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-IOF wheels were: 26.0% dry mist at 25 turns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

Example 18: Comparative Example of Coating and Primer Composition

A commercially available SDC MP1154D (SDC Technologies Inc., Anaheim, CA), a coating representative, described in United States Patent No. 6,001,263, was applied by flow coating onto a 0.63 cm (1/2-inch) polycarbonate plate. 4 inches) started thickness PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 0.39% dry mist at 50 turns and 0.78% dry mist after 200 turns. Topcoat thickness was 3.0 microns. The coated sample was placed in an oven according to the thermoforming procedure outlined here. At 165 ° C, the coating cracked before it could be placed in a cylindrical mandrel.

Example 19: Comparative Example of Coating and Primer Composition

A commercially available SDC MP1193A1 (SDC Technologies Inc., Anaheim, CA), a coatings representative, described in U.S. Patent No. 6,348,269, was applied by flow coating onto a 0.63 cm (1/2-inch) polycarbonate plate. 4 inches) started thickness PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-10F wheels were: 0.22% dry mist at 50 turns and 0.47% dry mist after 200 turns. The topcoat thickness was 5.0 microns. The coated sample was placed in an oven according to the thermoforming procedure outlined here. At 165 ° C, the coating cracked before it could be placed in a cylindrical mandrel.

Example 20: Comparative Example of Coating and Primer Composition

A commercially available SDC TC332 (SDC Technologies Inc., Anaheim, CA), a coating representative, described in United States Patent No. 5,013,608, was applied by flux coating onto a 0.63 cm (1/2-inch) polycarbonate plate. 4 inches) started thickness PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-IOF wheels were: 1.48% dry mist at 50 turns and 3.57% dry mist after 200 turns. Topcoat thickness was 3.5 microns. The coated sample was placed in an oven according to the thermoforming procedure outlined here. At 165 ° C, the coating cracked before it could be placed in a cylindrical mandrel.

Example 21: Anti-fog Coating Composition and Primer

1.91 grams of DI water was added dropwise to a stirring solution of 4.0 grams of A-187, 5.15 grams 15 of GF20, and 40.0 grams of glycol PM ether. The mixture was stirred at room temperature overnight. 0.74 grams of a sodium dioctyl sulfosuccinate surfactant in ethanol-water mixture (OT-75) Van Waters & Rogers Inc., Kirkland, WA) (75% solid) was added. The composition was stirred for two hours at room temperature and then cured in a room heated to 100 ° F for 3 weeks prior to coating application.

This coating composition was applied by flow coating on a 1/4 inch (250.63 cm) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. The surface coating was stored at 20 ° C and then subjected to saturated water vapor coated article at 60 ° C. The coated article became clear after 10 seconds and remained clear for at least one minute. Dry mist gain results from a Taber test using CS-10F wheels were: 1.6% dry mist at 50 turns and 9.0% dry mist after 200 turns. The top layer thickness was 3.2 microns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracking was observed within 4 inches.

Example 22: Anti-fog Coating Composition and Primer

2.11 grams of DI water was added dropwise to a stirring solution of 5.88 grams of A-18 7, 3.79 grams of GF20, and 3.9 grams of PM glycol ether. The mixture was stirred at room temperature overnight. 0.74 grams of OT-75 (75% solid) was added. The composition was stirred for two hours at room temperature and then cured at 100 ° F for 3 weeks prior to coating application.

This coating composition was applied by flow coating on a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. The surface coating was stored at 20 ° C and then subjected to saturated water vapor coated article at 60 ° C. The coated article became clear after 10 seconds and remained clear for at least one minute. Dry mist gain results from a Taber test using CS-10F wheels were: 4.8% dry mist at 50 turns and 33% dry mist after 200 turns. Topcoat thickness was 3.2 microns. Coating ability was assessed on a cylindrical mandrel and no cracking was observed within 4 words.

Example 23: Comparative Example of Anti-fog Coating Composition and Primer

A commercially available SDC AF1140 (SDC Technologies Inc., Anaheim, CA) was applied by flux coating onto a 0.63 cm (1/4 inch) initiated polycarbonate plate PR-1180. After drying in air for 30 minutes, the coating was cured for 2 hours at 130 ° C. The surface coating was stored at 20 ° C and then subjected to saturated water vapor at 60 ° C. The coated article became clear after 10 seconds and remained clear for at least 1 minute. Dry mist gain results from a Taber test using CS-10F wheels were: 3.20% dry mist at 50 turns and 14.3% dry mist after 200 turns. Topcoat thickness was 3.1 microns. The buildability of the coating was evaluated on a cylindrical mandrel and the crack was observed within a radius of less than 10 inches.

Example 24: Coating and primer that wear out over time

A weathering primer was prepared by mixing a poly (oxy-1,2-ethanediyl), alpha .- [3- [3- (2H-benzotriazo (-2-yl) -5- (1 -1-dimethylethyl) -4-hydroxyphenyl) -1-oxopropyl] - omega.- [3- [3 - [(2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) - 4-hydroxy phenyl] -1-oxopropoxy], 30-45 wt.% And poly (oxy-1,2-ethanediyl), alpha.- [3- [3- (2H-benzotriazo (-2-yl) - 5- (1,1-dimethylethyl) -4-hydroxyphenyl) -1-oxopropyl] -, omega-hydroxy, 40-55 wt% (Tinuvin 1130, Ciba Specialty Chemicals Corporation, Tarrytown, NY) in a commercially available PR1180 primer. Thereby 6.42 grams of Tinuvin1130 was added to 150 grams of PR1180. The resulting composition was allowed to stir for four hours before coating was applied.

This composition was applied as a primer by flow coating on a 0.63 cm (1/4 inch) polycarbonate plate. The primer was air dried for one hour before applying a topcoat of Example 7. The final coating was cured for 2 hours at 130 ° C. Dry mist gain results from a Taber test using CS-IOF wheels were: 2.0% dry mist at 50 turns and 11% dry mist after 200 turns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

The weatherability of the coating was evaluated by both QUV and Weather-O-Meter. The coating shows no adhesion and crack failure after 200 hours of exposure to ultraviolet light on both weather-accelerated wear testers. The QUV was operated under the condition of 8 hours of UV cycle at 70 ° C and 4 hour condensation cycle at 50 ° C. Weather-O-Meter was operated in accordance with ASTM 155-1.

Example 25: Weathering Coating and Primer 3.0 grams of Tinuvin1130 was added to 150 grams of PR1180. The resulting composition was allowed to stir for four hours before coating was applied.

This composition was applied as a flow coating primer on a 0.63 cm (1/4 inch) polycarbonate plate. The primer was air dried for one hour before applying a topcoat of Example 7. The final coating was cured for 2 hours at 130 ° C.

Dry mist gain results from a Taber test using CS-10F wheels were: 2.7% dry mist at 50 turns and 12% dry mist after 200 turns. The buildability of the coating was evaluated on a cylindrical mandrel and no cracks were observed within the 3 inch radius.

The weatherability of the coating was evaluated by both QUV and Weather-O-Meter. The coating shows no adhesion and crack failure after 200 hours of exposure to ultraviolet light in the two weather-accelerated wear testers. The QUV was operated under the condition of 8 hours UV cycle at 70 ° C and 4 hours condensation cycle at 50 ° C. The Weather-O-Meter was operated according to ASTM 155-1.

The weatherability of the coating was evaluated by both QUV and Weather-O-Meter. The coating shows no adhesion and crack failure after 200 hours of exposure to ultraviolet light on both weather-accelerated wear testers. The QUV was operated under the condition of 8 hours UV cycle at 70 ° C and 4 hours condensation cycle at 50 ° C. Weather-O-Meter was operated in accordance with ASTM 155-1.

Example 26: Coating which can be dyed and tinted on nylon lenses 26.4 grams of DI water were added dropwise to a stirring solution of 2.7 ± 2.7 grams of A188, 68.0 grams of GF20, and 147 grams of isopropanol. The mixture was stirred at room temperature overnight. 63 grams of PM glycol ether and 0.53 grams of a 10 wt% PA-57 solution in PM glycol ether were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing.

This coating composition was applied by dip coating to a nylon lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 3.5 microns, a Bayer number of 2.30, and excellent abrasion resistance. of steel wool. Some of the lenses were tinted by diluting a bottle of BPI tint (approximately 100 grams) to approximately 900 grams with DI water and brought to 96 ° C. The coated article was immersed in the heated solution for 30 minutes. The coated article was removed from the tint solution and light transmittance is measured using a BYK Gardner Haze-gard Plus dry mist meter. The coated article had around 11% light transmittance.

The wearability of coatings by atmospheric agents was evaluated by the B QDV method described in the descriptive report. The undyed coating showed adhesion failure after 96 hours of exposure. The dyed coating showed no adhesion or crack failure after 120 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour cycles of UV-B exposure (0.8 W / m2 / nm) with a panel temperature of 48 ° C and 4 hours of condensation with a panel temperature of 50 ° C.

Example 27: Coating that can be dyed having an isocyanate blocked in nylon / CR-3 lenses 5.93 grams of DI water was added dropwise to a 11.9 grams stirring solution of A-18 7, 15, 2 grams of GF20, and 32.5 grams of isopropanol. The mixture was stirred at room temperature overnight. 19 grams of PM glycol ether, 2.61 grams of BL 3175A, and 0.12 grams of a PA-57 solution, 10 wt% in PM glycol ether, were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing.

This coating composition was applied by dip coating to a nylon lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 4.0 microns, a Bayer number of 2.36, excellent wool abrasion resistance. steel, and around 10% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was assessed by method B of QUV according to the procedure in the descriptive report. Both dyed and undyed coating showed no adhesion and crack failure after 120 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour cycles of UV-B exposure (0.8 W / m2 / nm) with a panel temperature of 48 ° C and 4 hours of condensation with a panel temperature of 50 ° C.

This coating composition was applied by dip coating to a cauterized CR-39 lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 3.8 microns, a Bayer number of 1.93, excellent abrasion resistance of steel wool, and around 16% light transmittance after 30 min. Pretending. The weathering ability of the coatings by atmospheric agents was evaluated by method B of QUV according to the procedure in the descriptive report. Both dyed and non-dyed coating showed no adhesion failure after 72 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour cycles of UV-B exposure (0.8 W / m2 / nm) with a panel temperature of 48 ° C and 4 hours of condensation with a panel temperature of 50 ° C.

Example 28: Coating that can be dyed having a blocked isocyanate and dyeing in nylon lenses 26.4 grams of DI water were added dropwise to a stirring solution of 52.7 grams of A-187, 68.0 grams of GF20. , and 73.5 grams of isopropanol. The mixture was stirred at room temperature overnight. 157 grams of PM glycol ether, 11.8 grams of BL 3175A, and 0.53 grams of a PA-57 solution, 10 wt% in PM glycol ether, were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing. This coating composition was applied by dip coating to a nylon lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 5.2 microns, a Bayer number of 2.38, excellent wool abrasion resistance. steel, and around 12% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was assessed by method B of QUV according to the procedure in the descriptive report. Both dyed and undyed coating showed no adhesion and crack failure after 120 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour UV-B (0.8 W / m2 / nm) exposure cycles with a panel temperature of 48 ° C and 4 hours of condensation with a 50 ° C.

Example 29: Tintable coating having an isocyanate blocked in nylon lenses

260 grams of DI water was added dropwise to a stirring solution of 211 grams of A-187, 272 grams of GF20, and 764 grams of glycol PM ether. The mixture was stirred at room temperature overnight. 7.2 grams of BL 3175A and 2.12 grams of a 10 wt% solution of PA-57 in MW glycol ether were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing.

This coating composition was applied by dip coating to a nylon lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 4.9 microns, a Bayer number of 2.33, excellent abrasion resistance of steel wool, and around 25% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was assessed by method B of QUV according to the procedure in the descriptive report. Both dyed and undyed coating showed no adhesion and crack failure after 120 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour UV-B (0.8 W / m2 / nm) exposure cycles with a panel temperature of 48 ° C and 4 hours of condensation with a 50 ° C.

Example 30: Coating that can be dyed having a blocked isocyanate - Nylon / Trivex / ADC / MR® Lens 87.0 grams DI water was added dropwise to a stirring solution of 52.7 grams A-187.68 .0 grams of GF20, and 87.0 grams of PM glycol ether. The mixture was stirred at room temperature overnight. 78.0 grams of PM glycol ether, 11.8 grams of BL 3175A, and 0.53 grams of a PA-57 solution, 10 wt% in PM glycol ether, were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing.

This coating composition was applied by dip coating to a nylon lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 5.1 microns, a Bayer number of 2.48, excellent abrasion resistance of steel wool, and around 24% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was assessed by method B of QUV according to the procedure in the descriptive report. Both dyed and undyed coating showed no adhesion and crack failure after 120 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour cycles of UV-B exposure (0.8 W / m2 / nm) with a panel temperature of 48 ° C and 4 hours of condensation with a panel temperature of 50 ° C.

The wearability of the coatings by atmospheric agents was evaluated by method A of QUV according to the procedure in the descriptive report. Both the dyed and non-dyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-B exposure (0.8 W / m2 / nm) and 4 hours of condensation with a panel temperature of 55 ° C.

This coating composition was applied by dip coating to a Trivex ™ lens (obtained under the tradename Trilogy® from Younger Optics, Torrance, California) at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 5.4 microns, a Bayer number of 2.24, excellent wool abrasion resistance. around 20% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was evaluated by method A of QUV according to the procedure in the descriptive report. Both dyed and undyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-B exposure (0.8 W / m2 / nm) and 4 hours of condensation with a panel temperature of 55 ° C.

This coating composition was applied by dip coating to an ADC lens (CR-39) at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 5.2 microns, a Bayer number of 2.02, excellent abrasion resistance of steel wool, and around 29% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was evaluated by method A of QUV according to the procedure in the descriptive report. Both dyed and undyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-B exposure (0.8 W / m2 / nm) and 4 hours of condensation with a panel temperature of 55 ° C. This coating composition was applied by dip coating to an MR® lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 5.01 microns, excellent abrasion resistance of steel wool, and around 4 ° C. 5% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was evaluated by method A of QUV according to the procedure in the descriptive report. The undyed coating showed no adhesion and crack failure after 160 hours of exposure. The dyed coating showed adhesion failure after 112 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-B exposure (0.8 W / m2 / nm) and 4 hours of condensation with a panel temperature of 55 ° C.

Example 31: Coating that can be dyed having a blocked isocyanate

87.0 grams of DI water was added dropwise to a stirring solution of 63.2 grams of A-187, 61.2 grams of GF20, and 87.0 grams of glycol ether PM. The mixture was stirred at room temperature overnight. 78.0 grams of PM glycol ether, 11.8 grams of BL 3175A and 0.60 grams of a PA-57 solution, 10 wt% in PM glycol ether, were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing.

This coating composition was applied by dip coating to a nylon lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 5.7 microns, a Bayer number of 2.41, excellent wool abrasion resistance. of steel, and around 23% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was assessed by method B of QUV according to the procedure in the descriptive report. Both dyed and undyed coating showed no adhesion and crack failure after 120 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour cycles of UV-B exposure (0.8 W / m2 / nm) with a panel temperature of 48 ° C and 4 hours of condensation with a panel temperature of 50 ° C.

Example 32: Dyeable Coating Composition Having a Blocked Isocyanate

87.0 grams of DI water was added dropwise to a stirring solution of 73.7 grams of A-187, 47.6 grams of GF20, and 8.0 grams of glycol ether PM. The mixture was stirred at room temperature overnight. 8.0 grams of PM glycol ether, 11.8 grams of BL 3175A, and 0.60 grams of a 10% by weight solution of PA-57 in PM glycol ether were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing.

This coating composition was applied by dip coating to a nylon lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 5.7 microns, a Bayer number of 2.28, excellent wool abrasion resistance. around 15% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was assessed by method B of QUV according to the procedure in the descriptive report. Both dyed and undyed coating showed no adhesion and crack failure after 120 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour cycles of UV-B exposure (0.8 W / m2 / nm) with a panel temperature of 48 ° C and 4 hours of condensation with a panel temperature of 50 ° C.

The wearability of the coatings by atmospheric agents was evaluated by method A of QUV according to the procedure in the descriptive report. Both the dyed and non-dyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-B exposure (0.8 W / m2 / nm) and 4 hours of condensation with a panel temperature of 55 ° C.

This coating composition was applied by dip coating to a Trivex ™ lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 5.06 microns, a Bayer number of 2.2, excellent abrasion resistance of steel wool, and around -3.6% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was evaluated by method A of QUV according to the procedure in the descriptive report. Both the dyed and non-dyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-B exposure (0.8 W / m2 / nm) and 4 hours of condensation with a panel temperature of 55 ° C.

This coating composition was applied by dip coating to an ADC lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 5.15 microns, a Bayer number of 1.83, excellent wool abrasion resistance. steel, and around 17% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was evaluated by method A of QUV according to the procedure in the descriptive report. Both dyed and undyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-B exposure (0.8 W / m2 / nm) and 4 hours of condensation with a panel temperature of 55 ° C.

This coating composition was applied by dip coating to an MR® lens at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 4.89 microns, excellent abrasion resistance to steel wool, and around 33% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was evaluated by method A of QUV according to the procedure in the descriptive report. The undyed coating showed no adhesion and crack failure after 160 hours of exposure. The dyed coating showed adhesion failure after 112 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-B exposure (0.8 W / m2 / nm) and 4 hours of condensation with a panel temperature of 55 ° C.

Example 33: Dyed / Primer Coating The coating composition of Example 30 was applied by dip coating at a withdrawal rate of 12 æm to a PR-1135 initiated polycarbonate lens which was coated by rate immersion. 5 ipm withdrawal. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a Bayer number of 2.24, excellent steel wool abrasion resistance, and around 6 ° C. 5% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was assessed by method B of QUV according to the procedure in the descriptive report. The undyed coating showed adhesion failure after 120 hours of exposure. The dyed coating showed no adhesion or crack failure after 120 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour cycles of UV-B exposure (0.8 W / m2 / nm) with a panel temperature of 48 ° C and 4 hours of condensation with a panel temperature of 50 ° C.

The wearability of the coatings by atmospheric agents was also evaluated by method A of QUV according to the procedure in the descriptive report. Both the dyed and non-dyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of exposure to UV-A (0.8 W / mVnm) and 4 hours of condensation with a panel temperature of 55 ° C.

Example 34: Primer having a dyed cross-linking / coating agent

6.0 grams of BI7986 was added to 400 grams of PR-1135 primer. The resulting composition was allowed to stir for one hour at room temperature. This composition was applied as a dip coating primer at a withdrawal rate of 5 ipm to a polycarbonate lens. The primer was air dried for 30 min. prior to application of a coating composition of example 30. The coating composition of example 30 was applied by dip coating at a withdrawal rate of 12 µm. After air drying for 30 minutes, the final coating composition was cured for 2 hours at 1120 ° C to provide a cured film having a Bayer number of 2.24, excellent abrasion resistance to steel wool, and around 7 ° C. 9% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was assessed by method B of QUV according to the procedure in the descriptive report. The undyed coating showed adhesion failure after 120 hours of exposure. The dyed coating showed no adhesion or crack failure after 120 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour UV-B (0.8 W / m2 / nm) exposure cycles with a panel temperature of 480C and 4 hours of condensation with a temperature of 50 ° C panel.

The wearability of the coatings by atmospheric agents was also evaluated by method A of QUV according to the procedure in the descriptive report. Both the dyed and non-dyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-A (0.8 W / m2 / nm) exposure and 4 hours of condensation with a panel temperature of 55 ° C.

Example 35: Primer Having a Dyed Crosslinking / Coating Agent

12.0 grams of BI7986 was added to 400 grams of PR-1135 primer. The resulting composition was allowed to stir for one hour at room temperature. This composition was applied as a dip coating primer at a withdrawal rate of 5 ipm to a polycarbonate lens. The primer was air dried for 30 min. prior to applying a composition of an example 30 topcoat. The coating composition of example 30 was applied by dip coating at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the final coating composition was cured for 2 hours at 1120 ° C to provide a cured film having a Bayer number of 2.24, excellent abrasion resistance to steel wool, and around 7 ° C. 4% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was assessed by method B of QUV according to the procedure in the descriptive report. The undyed coating showed adhesion failure after 120 hours of exposure. The dyed coating showed no adhesion and crack failure after 120 hours of exposure. For test method B, the QUV unit is set to repeat 4-hour UV-B (0.8 W / m2 / nm) exposure cycles with a panel temperature of 48 ° C and 4 hours of condensation with a 50 ° C.

The wearability of the coatings by atmospheric agents was also evaluated by method A of QUV according to the procedure in the descriptive report. Both the dyed and non-dyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-A (0.8 W / m2 / nm) exposure and 4 hours of condensation with a panel temperature of 55 ° C.

Example 36: Primer Having a Dyed Crosslinking / Coating Agent

The primer composition of Example 35 was applied by dip coating at a 5 µm withdrawal rate to a polycarbonate lens. The primer was air dried for 30 minutes before applying an example 32 topcoat. The coating composition of example 32 was applied by dip coating at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a Bayer number of 2.15, excellent abrasion resistance to steel wool, and around 20 ° C. % light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was evaluated by method A of QUV according to the procedure in the descriptive report. Both the dyed and non-dyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-A (0.8 W / m2 / nm) exposure and 4 hours of condensation with a panel temperature of 55 ° C.

Example 37: Primer having a dyed cross-linking / coating agent 18.0 grams of BI7986 was added to 400 grams of PR-1135 primer. The resulting composition was allowed to stir for one hour at room temperature. This composition was applied as a dip coating primer at a withdrawal rate of 5 ipm to a polycarbonate lens. The primer was air dried for 30 min. before applying an example 30 topcoat. The coating composition of example 30 was applied by dip coating at a withdrawal rate of 12 ipm. After air drying for 30 minutes, the final coating composition was cured for 2 hours at 112 ° C to provide a cured film having a Bayer number of 2.24, excellent abrasion resistance to steel wool, and around 8 ° C. , 4% light transmittance after 30 min. of dyeing according to the procedure of Example 26. The wearability of coatings by the action of atmospheric agents was assessed by method B of QUV according to the procedure in the descriptive report. The undyed coating showed adhesion failure after 120 hours of exposure. The dyed coating showed no adhesion or crack failure after 120 hours of exposure without adhesion and crack failure. For test method B, the QUV unit is set to repeat 4-hour cycles of UV-B exposure (0.8 W / m2 / nm) with a panel temperature of 48 ° C and 4 hours of condensation with a panel temperature of 50 ° C.

The wearability of the coatings by atmospheric agents was also evaluated by method A of QUV according to the procedure in the descriptive report. Both the dyed and non-dyed coating showed no adhesion and crack failure after 160 hours of exposure. For test method A, the QUV unit is set to repeat cycles of 4 hours of UV-A (0.8 W / m2 / nm) exposure and 4 hours of condensation with a panel temperature of 55 ° C.

Example 38: Comparative Example of Coating Having Nylon Lens Blocked Isocyanate

87.0 grams of DI water was added dropwise to a stirring solution of 52.7 grams of A-187, 29.0 grams of itaconic acid and 87.0 grams of PM glycol ether. The mixture was stirred at room temperature overnight. 78.0 grams of PM glycol ether, 11.8 grams of BL 3175A, and 0.53 grams of a PA-57 solution, 10 wt% in PM glycol ether, were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing. This coating composition was applied by dip coating on a nylon lens at a withdrawal rate of 20 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C. A severe foggy film was obtained.

Example 39: Comparative Example of Nylon Lens Blocked Isocyanate Coating

87.0 grams of DI water was added dropwise to a stirring solution of 52.7 grams of A-187, 7.25 grams of itaconic acid and 87.0 grams of PM glycol ether. The mixture was stirred at room temperature overnight. 78.0 grams of PM glycol ether, 11.8 grams of BL 3175A, and 0.53 grams of a PA-57 solution, 10 wt% in PM glycol ether, were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing. This coating composition was applied by dip coating on a nylon lens at a withdrawal rate of 20 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 2.5 microns, a Bayer number of 1.22, wool abrasion resistance. bad steel, and 3.7% light transmittance after 30 min. and dyeing. Example 40: Comparative Example of Coating Having Nylon Lens Blocked Isocyanate

87.0 grams of DI water was added dropwise to a stirring solution of 52.7 grams of A-187, 22.3 grams of succinic anhydride and 87.0 grams of PM glycol ether. The mixture was stirred at room temperature overnight. 78.0 grams of PM glycol ether, 11.8 grams of BL 3175A, and 0.53 grams of a PA-57 solution, 10 wt% in PM glycol ether, were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing. This coating composition was applied by dip coating on a nylon lens at a withdrawal rate of 20 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C. A severe foggy film was obtained.

Example 41: Comparative Example of Nylon Lens Blocked Isocyanate Coating

87.0 grams of DI water was added dropwise to a stirring solution of 52.7 grams of A-187, 5.57 grams of succinic anhydride and 87.0 grams of PM glycol ether. The mixture was stirred at room temperature overnight. 78.0 grams of PM glycol ether, 11.8 grams of BL 3175A, and 0.53 grams of a PA-57 solution, 10 wt% in PM glycol ether, were added. The composition was allowed to stir for an additional 20 minutes after addition to ensure mixing. This coating composition was applied by dip coating on a nylon lens at a withdrawal rate of 20 ipm. After air drying for 30 minutes, the coating composition was cured for 2 hours at 112 ° C to provide a cured film having a thickness of approximately 2.5 microns, a Bayer number of 0.56, wool abrasion resistance. bad steel, and 3.2% light transmittance after 30 min. and dyeing.

It will be understood that various changes may be made without departing from the scope of the invention, which should not be construed as limited to what is described in the description.

Claims (43)

A composition which, when applied to a substrate and cured, provides a transparent coating that can be dyed on the substrate comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of at least one epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein at least one of epoxy functional silane and diol functional organopolysiloxane is present at a molar ratio to the multifunctional crosslinker. about 10: 1 to about 1:10; an amount of water sufficient to hydrolyze at least one between epoxy functional silane and diol functional organopolysiloxane and multifunctional crosslinker; and a blocked isocyanate. Composition according to Claim 1, characterized in that at least one of epoxy functional silane and diol functional organopolysiloxane is present in a multifunctional crosslinker molar ratio of from about 6: 1 to about 1: 6. Composition according to Claim 1, characterized in that at least one of epoxy functional silane and diol functional organopolysiloxane is present in a molar ratio to the multifunctional crosslinker of from about 3: 1 to about -1: 3. . Composition according to Claim 1, characterized in that the blocked isocyanate comprises approximately 1% by weight to approximately 30% by weight of the solids of the coating composition. Composition according to Claim 1, characterized in that the blocked isocyanate comprises approximately 2% by weight to approximately 15% by weight of the solids of the coating composition. Composition according to Claim 1, characterized in that the blocked isocyanate comprises approximately 3% by weight to approximately 10% by weight of the solids of the coating composition. Composition according to Claim 1, characterized in that the blocked isocyanate is selected from at least one of Desmodur Bl 3175, Desmodur Bl 3272, Desmodur Bl 3370, Desmodur Bl 3475, Desmodur Bl 4265, Trixene Bl 7982, Trixene Bl 7983, Trixene Bl 7984, Trixene Bl 7980, Trixene Bl 7960, and Trixene Bl -7950. Composition according to Claim 1, characterized in that the blocked isocyanate comprises Desmodur Bl 3175. Composition according to Claim 1, characterized in that the coating has a Bayer number greater than approximately 1.5. Composition according to Claim 1, characterized in that the coating has a Bayer number greater than approximately 2. Composition according to Claim 1, characterized in that the coating has no adhesion or cracking failure according to the test conditions of method QUV A and method QUV B for at least 72 hours. Composition according to Claim 1, characterized in that the coating has no adhesion or cracking failure according to the test conditions of method QUV A and method QUV B for at least 120 hours. Composition according to Claim 1, characterized in that the constituent solvent of the aqueous-organic solvent mixture consists of approximately 40 to approximately 98% by weight of the composition. Composition according to Claim 1, characterized in that the constituent solvent of the aqueous-organic solvent mixture is selected from an ether, glycol or glycol ether, a ketone, an ester, a glycol acetate. ether, alcohols having the formula ROH where R is an alkyl group containing from 1 to about 10 carbon atoms, and mixtures thereof. Composition according to Claim 1, characterized in that the constituent solvent of the aqueous-organic solvent mixture is selected from glycols, ethers, glycol ethers having the formula R1- (OR2) x -OR1 where x is 0, 1, 2, 3 or 4, R1 is hydrogen or an alkyl group containing from 1 to about 10 carbon atoms and R2 is an alkylene group containing from 1 to about 10 carbon atoms and combinations thereof. Composition according to Claim 1, characterized in that it further comprises at least one of tetrafunctional silanes, disilanes and alkyl silanes. Composition according to Claim 1, characterized in that it further comprises colloidal silica. Composition according to Claim 1, characterized in that the epoxy functional silane is represented by the formula R3xSi (OR4) 4-x, where: χ is an integer of 1, 2 or 3; R3 is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms and having at least 1 functional group epoxy; R4 is H, an alkyl group containing from 1 approximately 5 carbon atoms, an acetyl group, a -Si (OR5) 3-yR6y group where y is an integer of 0, 1, 2 or 3, and combinations of the same; R5 is H, an alkyl group containing from 1 to about 5 carbon atoms, an acetyl group, or other group -Si (OR5) 3 -yR6y and combinations thereof; and R 6 is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms. A composition which, when applied to a substrate and cured, provides a transparent coating that can be dyed on the substrate comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of a diol-functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and where the diol functional organopolysiloxane is present at a molar to multifunctional crosslinker ratio of approximately 10: 1 to 1. : 10; sufficient water to hydrolyze the diol functional organopolysiloxane and the multifunctional crosslinker; and a blocked isocyanate. Composition according to Claim 19, characterized in that the organic aqueous solvent mixture further comprises hydrolysis products and partial condensates of an epoxy functional silane and at least one multifunctional crosslinker. An article comprising: a dyeable substrate and coating formed on at least one substrate surface by curing a coating composition comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of at least one between epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein at least one between epoxy functional silane and diol functional organopolysiloxane is present in a molar ratio for multifunctional crosslinker from approximately 10: 1 to 1:10; an amount of water sufficient to hydrolyze at least one between epoxy functional silane and diol functional organopolysiloxane and the multifunctional crosslinker; and a blocked isocyanate. An article according to claim 21 further comprising at least one primer arranged on at least one substrate surface between the substrate and the coating. Article according to Claim 22, characterized in that at least one primer comprises a polyurethane dispersion-based primer. An article according to claim 22, characterized in that at least one primer comprises a polyurethane dispersion based primer having a crosslinking agent. Article according to Claim 24, characterized in that the cross-linking agent is selected from a blocked isocyanate, aziridine resin, epoxy resin, and melamine resin. An article according to claim 24, characterized in that the polyurethane dispersion-based primer further comprises an ultraviolet light absorber. Article according to Claim 24, characterized in that the cross-linking agent comprises from about 1% to about 30% by weight of the polyurethane dispersion-based primer solids. Article according to Claim 21, characterized in that the dyeable coating has a thickness between approximately 0.2 μm and approximately 20 μm. Article according to Claim 21, characterized in that the dyeable coating has a thickness between approximately 1.5 μm and approximately 10 μm. Article according to Claim 21, characterized in that the dyeable coating has a thickness between approximately 2.5 μm and approximately 7 μm. Article according to claim 21, characterized in that the substrate is selected from acrylic polymers, poly (ethylene terephthalate), polycarbonates, polyamides, polyimides, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, chloride. of polyvinyl, butyrates, and poly (diethylene glycol bis-allyl carbonate). Article according to Claim 31, characterized in that the substrate comprises a lens. 33. An article comprising: a dyeable substrate and coating formed on at least one surface of the substrate by curing a coating composition comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of an organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the diol functional organopolysiloxane is present at a molar ratio to the multifunctional crosslinker of approximately 10: 1 to 1:10; sufficient water to hydrolyze the diol functional organopolysiloxane and the multifunctional crosslinker; and a blocked isocyanate. Article according to Claim 33, characterized in that the coating composition includes at least one of tetrafunctional silane and disilane, and wherein the epoxy functional silane is present in a molar ratio to at least one of silane. tetrafunctional and disilane of at least approximately 5.5: 1. 35. An article comprising: a substrate, a primer arranged on at least one surface of the substrate, and a dyeable coating formed on at least a portion of the primer curing a coating composition, wherein: the coating composition comprises : an aqueous-organic solvent mixture having hydrolysis and partial condensate products of at least one epoxy functional silane and a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein at least one of epoxy functional silane and diol functional organopolysiloxane is present in a multifunctional crosslinker molar ratio of from about 10: 1 to 1:10; and an amount of water sufficient to hydrolyze at least one between epoxy functional silane and diol functional organopolysiloxane and multifunctional crosslinker; and the primer comprises a polyurethane dispersion based primer having a crosslinking agent. Article according to claim 35, characterized in that the dyeable coating does not exhibit adhesion or cracking failure according to the test conditions of method QUV A and method QUV B for at least approximately 72 hours. . 37. An article comprising: a substrate, a primer arranged on at least one surface of the substrate, and a dyeable coating formed on at least a portion of the primer curing a coating composition, wherein: the coating composition comprises : an aqueous-organic solvent mixture having hydrolysis products and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the diol functional organopolysiloxane is present in a molar to multifunctional crosslinker ratio of from about 10: 1 to 1:10; an amount of water sufficient to hydrolyze the diol functional organopolysiloxane and multifunctional crosslinker; The primer comprises a polyurethane dispersion based primer having a crosslinking agent. 38. The process for dyeing a dyed, abrasion-resistant transparent coating that is coated on at least one surface of a substrate, comprising: contacting at least one surface of a substrate with a coating composition which forms a coating. abrasion-resistant clear coating, which may be dyed after curing, the coating composition comprising: an aqueous-organic solvent mixture having hydrolysis products and partial condensates of at least one between epoxy functional silane and diol functional organopolysiloxane and at at least one multifunctional crosslinker, wherein the multifunctional crosslinker comprises a multifunctional anhydride, wherein the multifunctional crosslinker comprises a silylated multifunctional anhydride, and wherein at least one of epoxy functional silane and diol functional organopolysiloxane is present at a molar ratio to the approach multifunctional crosslinker between 10: 1 to 1:10; and an amount of water sufficient to hydrolyze at least one of the epoxy functional silane and diol functional organopolysiloxane and multifunctional crosslinker; curing the coating composition on the substrate to form a dyed, abrasion resistant curable transparent coating; and dyeing the cured coating by dipping the coated surface of the substrate in a dye bath for a period of time sufficient for the cured coating to absorb or transmit to the substrate a desired amount of dye. Process according to Claim 38, characterized in that the coating composition further comprises a blocked isocyanate. The method of claim 38 further comprising applying a primer to the substrate before applying the coating composition to the substrate in the primer. Process according to Claim 40, characterized in that the primer comprises a polyurethane dispersion-based primer. Process according to Claim 40, characterized in that the primer comprises a polyurethane dispersion-based primer having a cross-linking agent. 43 A process for dyeing an abrasion-resistant, dyeable transparent coating which is coated on at least one surface of a substrate, comprising: contacting at least one surface of a substrate with a coating composition forming a resistant transparent coating abrasion, which may be dyed after curing, the coating composition comprising: an aqueous-organic solvent mixture having hydrolysis and partial condensates of a diol functional organopolysiloxane and at least one multifunctional crosslinker, wherein the multifunctional crosslinker is selected from multifunctional carboxylic acids, multifunctional anhydrides, and silylated multifunctional anhydrides, and wherein the diol functional organopolysiloxane is present in a multifunctional crosslinker molar ratio of approximately 10: 1 to 1:10; and an amount of water sufficient to hydrolyze the diol functional organopolysiloxane and the multifunctional crosslinker; curing the coating composition on the substrate to form a dyed, abrasion resistant curable transparent coating; and dyeing the cured coating by dipping the coated surface of the substrate in a dye bath for a period of time sufficient for the cured coating to absorb or transmit to the substrate a desired amount of dye.